Plasticized Polyolefin Compositions

ABSTRACT

The present invention relates to plasticized polyolefin compositions comprising a polyolefin and a non-functionalized hydrocarbon plasticizer.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.U.S. Ser. No. 60/402,665, filed Aug. 12, 2002, and U.S. Ser. No. “NotYet Assigned” filed Aug. 4, 2003, (our Case No. 2002B107A) and PCTApplication No. “Not Yet Assigned”, filed Aug. 4, 2003 (our Case No.2002B107A) the disclosures of which are incorporated by reference.

FIELD OF THE INVENTION

The present invention relates to plasticized polyolefins comprising apolyolefin and a non-functionalized plasticizer. More particularly, thepresent invention relates to plasticized polyolefins such as propylenepolymers and or butene polymers having improved properties such asprocessability, flexibility, softness, and impact resistance.

BACKGROUND OF THE INVENTION

Polyolefins are useful in any number of everyday articles. However, onedrawback to many polyolefins, especially propylene homopolymers and somepropylene copolymers, is their relatively high glass transitiontemperature. This characteristic makes these polyolefins brittle,especially at low temperatures. Many applications of polyolefins benefitfrom having useful properties over a broad range of temperatures;consequently, there is a need to provide polyolefins that can maintaindesirable characteristics such as high or low temperature performance,etc., while maintaining or improving upon the impact strength andtoughness at lower temperatures. In particular, it would be advantageousto provide a propylene polymer possessing improved toughness and or highuse temperature without sacrificing its other desirable properties.

Addition of a plasticizer or other substance to a polyolefin is one wayto improve such properties as impact strength and toughness. Some patentdisclosures directed to such an end are U.S. Pat. No. 4,960,820; U.S.Pat. No. 4,132,698; U.S. Pat. No. 3,201,364; WO 02/31044; WO 01/18109A1; and EP 0 300 689 A2. These disclosures are directed to polyolefinsand elastomers blended with functionalized plasticizers. Thefunctionalized plasticizers are materials such as mineral oils whichcontain aromatic groups, and high (greater than −20° C.) pour pointcompounds. Use of these compounds typically does not preserve thetransparency of the polyolefin, and impact strength is often notimproved.

WO 98/44041 discloses plastic based sheet like material for a structure,especially a floor covering, which contains in a blend a plastic matrixcomprising a chlorine free polyolefin or mixture of polyolefins and aplasticizer characterized in that the plasticizer is an oligomericpolyalphaolefin type substance.

Other background references include EP 0 448 259 A, EP 1 028 145 A, U.S.Pat. Nos. 4,073,782, and 3,415,925.

What is needed is a polyolefin with lower flexural modulus, lower glasstransition temperature, and higher impact strength near and below 0° C.,while not materially influencing the peak melting temperature of thepolyolefin, the polyolefin crystallization rate, or its clarity, andwith minimal migration of plasticizer to the surface of fabricatedarticles. A plasticized polyolefin according to this invention canfulfill these needs. More specifically, there is a need for aplasticized polypropylene that can be used in such applications as foodcontainers and toys.

Likewise, a plasticized polyolefin with improved softness, betterflexibility (lower flexural modulus), a depressed glass transitiontemperature, and or improved impact strength (improved Gardner impact)at low temperatures (below 0° C.), where the melting temperature of thepolyolefin, the polyolefin crystallization rate, or its clarity are notinfluenced and with minimal migration of the plasticizer to the surfaceof articles made therefrom is desirable.

It would be particularly desirable to plasticize polyolefins by using asimple, non-reactive compound such as a paraffin. However, it has beentaught that aliphatic or paraffinic compounds would impair theproperties of polyolefins, and was thus not recommended. (See, e.g.,CHEMICAL ADDITIVES FOR PLASTICS INDUSTRY 107-116 (Radian Corp., NoyesData Corporation, NJ 1987); WO 01/18109 A1).

Mineral oils, which have been used as extenders, softeners, and the likein various applications, consist of thousands of different compounds,many of which are undesirable in a lubricating system. Under moderate tohigh temperatures these compounds can volatilize and oxidize, even withthe addition of oxidation inhibitors.Certain mineral oils, distinguished by their viscosity indices and theamount of saturates and sulfur they contain, have been classified asHydrocarbon Basestock Group I, II or III by the American PetroleumInstitute (API). Group I basestocks are solvent refined mineral oils.They contain the most unsaturates and sulfur and have the lowestviscosity indices. They define the bottom tier of lubricant performance.Group I basestocks are the least expensive to produce, and theycurrently account for abut 75 percent of all basestocks. These comprisethe bulk of the “conventional” basestocks. Groups II and III are theHigh Viscosity Index and Very High Viscosity Index basestocks. They arehydroprocessed mineral oils. The Group III oils contain less unsaturatesand sulfur than the Group I oils and have higher viscosity indices thanthe Group II oils do. Additional basestocks, named Groups IV and V, arealso used in the basestock industry. Rudnick and Shubkin describe thefive basestock Groups as typically being:Group I—mineral oils refined using solvent extraction of aromatics,solvent dewaxing, hydrofining to reduce sulfur content to producemineral oils with sulfur levels greater than 0.03 weight %, saturateslevels of 60 to 80% and a viscosity index of about 90;Group II—mildly hydrocracked mineral oils with conventional solventextraction of aromatics, solvent dewaxing, and more severe hydrofiningto reduce sulfur levels to less than or equal to 0.03 weight % as wellas removing double bonds from some of the olefinic and aromaticcompounds, saturate levels are greater than 95-98% and VI is about80-120;Group III—severely hydrotreated mineral oils with saturates levels ofsome oils virtually 100%, sulfur contents are less than or equal to 0.03weight % (preferably between 0.001 and 0.01%) and VI is in excess of120;Group IV—poly-alpha-olefins-hydrocarbons manufactured by the catalyticoligomerization of linear olefins having 6 or more carbon atoms. Inindustry however, the Group IV basestocks are referred to as“polyalphaolefins” are generally thought of as a class of syntheticbasestock fluids produced by oligomerizing C₄ and greater alphaolefins;andGroup V—esters, polyethers, polyalkylene glycols, and includes all otherbasestocks not included in Groups I, II, III and IV. (see SyntheticLubricants and High-Performance Functional Fluids, Second edition,Rudnick, Shubkin, eds., Marcel Dekker, Inc. New York, 1999.)Other references of interest include: U.S. Pat. No. 5,869,555, U.S. Pat.No. 4,210,570, U.S. Pat. No. 4,110,185, GB 1,329,915, U.S. Pat. No.3,201,364, U.S. Pat. No. 4,774,277, JP01282280, FR2094870, JP69029554,Rubber Technology Handbook, Werner Hoffman, Hanser Publishers, New York,1989, pg 294-305, Additives for Plastics, J. Stepek, H. Daoust, SpringerVerlag, New York, 1983, pg-6-69.U.S. Pat. No. 4,536,537 discloses blends of LLDPE (UC 7047),polypropylene (5520) and Synfluid 2CS, 4CS, or 6CS having a viscosity of4.0 to 6.5 cSt at 100° F./38° C., however the Synfluid 4CS and 8CS arereported to “not work” (col 3, ln 12).

SUMMARY OF THE INVENTION

This invention relates to plasticized polyolefin compositions comprisingone or more polyolefins and one or more non-functionalized plasticizers(“NFP”).

This invention relates to plasticized polyolefin compositions comprisingone or more polyolefins and one or more non-functionalized plasticizers(“NFP's”) where the non-functionalized plasticizer has a kinematicviscosity (“KV”) of 2 cSt or less at 100° C. For purposes of thisinvention if the NFP has a flash point of less than 100° C. it isdefined to have a KV at 100° C. of less than 2 cSt.

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer is apolyalphaolefin comprising oligomers of C₅ to C₁₄ olefins having aKinematic viscosity of 10 cSt or more at 100° C. and a viscosity indexof 120 or more.

This invention also relates to plasticized polypropylene compositionscomprising polypropylene and one or more non-functionalized plasticizerswhere the non-functionalized plasticizer comprises oligomers of C₅ toC₁₄ olefins having viscosity index of 120 or more, provided that whenthe plasticized composition comprises between 4 and 10 weight % ofpolyalphaolefin that is a hydrogenated, highly branched dimer of analpha olefin having 8-12 carbon atoms, the composition does notcomprises between 18 and 25 weight percent of a linear low densitypolyethylene having a density of 0.912 to 0.935 g/cc.This invention also relates to plasticized polypropylene compositionscomprising polypropylene and one or more non-functionalized plasticizerswhere the non-functionalized plasticizer comprises oligomers of C₆ toC₁₄ olefins having viscosity index of 120 or more, provided that whenthe composition does not comprises an impact copolymer of polypropyleneand 40-50 weight % of an ethylene propylene rubber or provided that thecomposition does not comprise a random copolymer of propylene andethylene.

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer comprises linearand or branched paraffinic hydrocarbon compositions produced by one ormore gas to liquids process having a number average molecular weight of500 to 20,000.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graphical representation of the Storage Modulus (E′) as afunction of temperature for various plasticized propylene homopolymerexamples cited herein;

FIG. 2 is a graphical representation of the Tan δ as a function oftemperature for various plasticized propylene homopolymer examples citedherein;

FIG. 3 is a graphical representation of the Tan δ as a function oftemperature for various plasticized propylene copolymer examples citedherein;

FIG. 4 is a graphical representation of the Tan δ as a function oftemperature for various plasticized propylene impact copolymer examplescited herein;

FIG. 5 is a graphical representation of the melting heat flow from DSCas a function of temperature for various plasticized propylenehomopolymer samples illustrative of the invention;

FIG. 6 is a graphical representation of the crystallization heat flowfrom DSC as a function of temperature for various samples plasticizedpropylene homopolymer samples illustrative of the invention;

FIG. 7 is a graphical representation of the melting heat flow from DSCas a function of temperature for various plasticized propylene copolymersamples illustrative of the invention;

FIG. 8 is a graphical representation of the crystallization heat flowfrom DSC as a function of temperature for various plasticized propylenecopolymer samples illustrative of the invention;

FIG. 9 is a graphical representation of the melting heat flow from DSCas a function of temperature for various plasticized propylene impactcopolymer samples illustrative of the invention;

FIG. 10 is a graphical representation of the crystallization heat flowfrom DSC as a function of temperature for various plasticized propyleneimpact copolymer samples illustrative of the invention;

FIG. 11 is a graphical representation of the shear viscosity as afunction of shear rate for various plasticized propylene homopolymersamples illustrative of the invention;

FIG. 12 is a graphical representation of the shear viscosity as afunction of shear rate for various plasticized propylene copolymersamples illustrative of the invention;

FIG. 13 is a graphical representation of the shear viscosity as afunction of shear rate for various plasticized propylene impactcopolymer samples illustrative of the invention; and

FIG. 14 is a graphical representation of the molecular weightdistribution for various plasticized propylene homopolymer samplesillustrative of the invention.

DEFINITIONS

For purposes of this invention and the claims thereto when a polymer oroligomer is referred to as comprising an olefin, the olefin present inthe polymer or oligomer is the polymerized or oligomerized form of theolefin, respectively. Likewise the use of the term polymer is meant toencompass homopolymers and copolymers. In addition the term copolymerincludes any polymer having 2 or more monomers. Thus, as used herein,the term “polypropylene” means a polymer made of at least 50% propyleneunits, preferably at least 70% propylene units, more preferably at least80% propylene units, even more preferably at least 90% propylene units,even more preferably at least 95% propylene units or 100% propyleneunits.

For purposes of this invention an oligomer is defined to have an Mn ofless than 21,000 g/mol, preferably less than 20,000 g/mol, preferablyless than 19,000 g/mol, preferably less than 18,000 g/mol, preferablyless than 16,000 g/mol, preferably less than 15,000 g/mol, preferablyless than 13,000 g/mol, preferably less than 10,000 g/mol, preferablyless than 5000 g/mol, preferably less than 3000 g/mol.

For purposes of this invention and the claims thereto Group I, II, andIII basestocks are defined to be mineral oils having the followingproperties:

Saturates (wt %) Sulfur (wt %) Viscosity Index Group I <90 &/or >0.03% &≧80 & <120 Group II ≧90 & ≦0.03% & ≧80 & <120 Group III ≧90 & ≦0.03% &≧120

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to plasticized polyolefin compositions comprisingone or more polyolefins and one or more non-functionalized plasticizers(“NFP”).

Typically, the polyolefin(s) are present in the compositions of thepresent invention at from 40 wt % to 99.9 wt % (based upon the weight ofthe polyolefin and the NFP) in one embodiment, and from 50 wt % to 99 wt% in another embodiment, and from 60 wt % to 98 wt % in yet anotherembodiment, and from 70 wt % to 97 wt % in yet another embodiment, andfrom 80 wt % to 97 wt % in yet another embodiment, and from 90 wt % to98 wt % in yet another embodiment, wherein a desirable range may be anycombination of any upper wt % limit with any lower wt % limit describedherein.

In another embodiment the plasticized polyolefin comprises polypropylenepresent at 50 to 99.99 weight %, alternately 60 to 99 weight %,alternately 70 to 98 weight %, alternately 80 to 97 weight %,alternately 90 to 96 weight %, and the NFP is present at 50 to 0.01weight %, alternately 40 to 1 weight %, alternately 30 to 2 weight %,alternately 20 to 3 weight %, alternately 10 to 4 weight %, based uponthe weight of the polypropylene and the NFP.

In another embodiment the plasticized polyolefin comprises polybutenepresent at 50 to 99.99 weight %, alternately 60 to 99 weight %,alternately 70 to 98 weight %, alternately 80 to 97 weight %,alternately 90 to 96 weight %, and the NFP is present at 50 to 0.01weight %, alternately 40 to 1 weight %, alternately 30 to 2 weight %,alternately 20 to 3 weight %, alternately 10 to 4 weight %, based uponthe weight of the polybutene and the NFP.

In another embodiment the polyolefin comprises polypropylene and orpolybutene and NFP is present at 0.01 to 50 weight %, more preferably0.05 to 45 weight %, more preferably 0.5 to 40 weight %, more preferably1 to 35 weight %, more preferably 2 to 30 weight %, more preferably 3 to25 weight %, more preferably 4 to 20 weight %, more preferably 5 to 15weight %, based upon the weight of the polypropylene and the NFP. Inanother embodiment, the NFP is present at 1 to 15 weight %, preferably 1to 10 weight %, based upon the weight of the polypropylene and orpolybutene and the NFP.

In another embodiment the NFP is present at more than 3 weight %, basedupon the weight of the polyolefin and the NFP.For purposes of this invention and the claims thereto the amount of NFPin a given composition is determined by the extraction techniquedescribed below as Method 1: Extraction. The CRYSTAF method alsodescribed is for comparison purposes.For purposes of this invention and the claims thereto when melting pointis referred to and there is a range of melting temperatures, the meltingpoint is defined to be the peak melting temperature from a DSC trace asdescribed below.

Non-Functionalized Plasticizer

The polyolefin compositions of the present invention include anon-functionalized plasticizer (“NFP”). The NFP of the present inventionis a compound comprising carbon and hydrogen, and does not include to anappreciable extent functional groups selected from hydroxide, aryls andsubstituted aryls, halogens, alkoxys, carboxylates, esters, carbonunsaturation, acrylates, oxygen, nitrogen, and carboxyl. By “appreciableextent”, it is meant that these groups and compounds comprising thesegroups are not deliberately added to the NFP, and if present at all, arepresent at less than 5 wt % by weight of the NFP in one embodiment, morepreferably less than 4 weight %, more preferably less than 3 weight %,more preferably less than 2 weight %, more preferably less than 1 weight%, more preferably less than 0.7 weight %, more preferably less than 0.5weight %, more preferably less than 0.3 weight %, more preferably lessthan 0.1 weight %, more preferably less than 0.05 weight %, morepreferably less than 0.01 weight %, more preferably less than 0.001weight %, based upon the weight of the NFP.

In one embodiment, the NFP comprises C₆ to C₂₀₀ paraffins, and C₈ toC₁₀₀ paraffins in another embodiment. In another embodiment, the NFPconsists essentially of C₆ to C₂₀₀ paraffins, and consists essentiallyof C₈ to C₁₀₀ paraffins in another embodiment. For purposes of thepresent invention and description herein, the term “paraffin” includesall isomers such as n-paraffins, branched paraffins, isoparaffins, andmay include cyclic aliphatic species, and blends thereof, and may bederived synthetically by means known in the art, or from refined crudeoil in such a way as to meet the requirements described for desirableNFPs described herein. It will be realized that the classes of materialsdescribed herein that are useful as NFPs can be utilized alone oradmixed with other NFPs described herein in order to obtain desiredproperties.

This invention further relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers (“NFP's”) where the non-functionalized plasticizer has akinematic viscosity (“KV”) of 2 cSt or less at 100° C., preferably 1.5cSt or less, preferably 1.0 cSt or less, preferably 0.5 cSt or less (asmeasured by ASTM D 445). In another embodiment the NFP having a KV of 2cSt or less at 100° C. also has a glass transition temperature (Tg) thatcannot be determined by ASTM E 1356 or if it can be determined then theTg according to ASTM E 1356 is less than 30° C. preferably less than 20°C., more preferably less than 10° C., more preferably less than 0° C.,more preferably less than −5° C., more preferably less than −10° C.,more preferably less than −15° C.

In another embodiment the NFP having a KV of 2 cSt or less at 100° C.,optionally having a glass transition temperature (Tg) that cannot bedetermined by ASTM ASTM E 1356 or if it can be determined then the Tgaccording to ASTM E 1356 is less than 30° C. preferably less than 20°C., more preferably less than 10° C., more preferably less than 0° C.,more preferably less than −5° C., has one or more of the followingproperties:

-   1. a distillation range as determined by ASTM D 86 having a    difference between the upper temperature and the lower temperature    of 40° C. or less, preferably 35° C. or less, preferably 30° C. or    less, preferably 25° C. or less, preferably 20° C. or less,    preferably 15° C. or less, preferably 10° C. or less, preferably    between 6 and 40° C., preferably between 6 and 30° C.; and or-   2. an initial boiling point as determined by ASTM D 86 greater than    100° C., preferably greater than 110° C., preferably greater than    120° C., preferably greater than 130° C., preferably greater than    140° C., preferably greater than 150° C., preferably greater than    160° C., preferably greater than 170° C., preferably greater than    180° C., preferably greater than 190° C., preferably greater than    200° C., preferably greater than 210° C., preferably greater than    220° C., preferably greater than 230° C., preferably greater than    240° C.; and or-   3. a pour point of 10° C. or less (as determined by ASTM D 97),    preferably 0° C. or less, preferably −5° C. or less, preferably    −15° C. or less, preferably −40° C. or less, preferably −50° C. or    less, preferably −60° C. or less; and or-   4. a specific gravity (ASTM D 4052, 15.6/15.6° C.) of less than    0.88, preferably less than 0.85, preferably less than 0.80,    preferably less than 0.75, preferably less than 0.70, preferably    from 0.65 to 0.88, preferably from 0.70 to 0.86, preferably from    0.75 to 0.85, preferably from 0.79 to 0.85, preferably from 0.800 to    0.840; and or-   5. a final boiling point as determined by ASTM D 86 of from 115° C.    to 500° C., preferably from 200° C. to 450° C., preferably from    250° C. to 400° C.; and or-   6. a weight average molecular weight (Mw) between 2,000 and 100    g/mol, preferably between 1500 and 150, more preferably between 1000    and 200; and or-   7. a number average molecular weight (Mn) between 2,000 and 100    g/mol, preferably between 1500 and 150, more preferably between 1000    and 200; and or-   8. a flash point as measured by ASTM D 56 of −30 to 150° C., and or-   9. a dielectric constant at 20° C. of less than 3.0, preferably less    than 2.8, preferably less than 2.5, preferably less than 2.3,    preferably less than 2.1; and or-   10. a density (ASTM 4052, 15.6/15.6° C.) of from 0.70 to 0.83 g/cm³;    and or-   11. a viscosity (ASTM 445, 25° C.) of from 0.5 to 20 cSt at 25° C.;    and or-   12. a carbon number of from 6 to 150, preferably from 7 to 100,    preferably 10 to 30, preferably 12 to 25.

In certain embodiments of the invention the NFP having a KV of 2 cSt orless at 100° C. preferably comprises at least 50 weight %, preferably atleast 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %,preferably at least 90 wt %, preferably at least 95 wt % preferably 100wt % of C₆ to C₁₅₀ isoparaffins, preferably C₆ to C₁₀₀ isoparaffins,preferably C₆ to C₂₅ isoparaffins, more preferably C₈ to C₂₀isoparaffins. By isoparaffin is meant that the paraffin chains possessC₁ to C₁₀ alkyl branching along at least a portion of each paraffinchain. More particularly, the isoparaffins are saturated aliphatichydrocarbons whose molecules have at least one carbon atom bonded to atleast three other carbon atoms or at least one side chain (i.e., amolecule having one or more tertiary or quaternary carbon atoms), andpreferably wherein the total number of carbon atoms per molecule is inthe range between 6 to 50, and between 10 and 24 in another embodiment,and from 10 to 15 in yet another embodiment. Various isomers of eachcarbon number will typically be present. The isoparaffins may alsoinclude cycloparaffins with branched side chains, generally as a minorcomponent of the isoparaffin. Preferably the density (ASTM 4052,15.6/15.6° C.) of these isoparaffins ranges from 0.70 to 0.83 g/cm³; thepour point is −40° C. or less, preferably −50° C. or less, the viscosity(ASTM 445, 25° C.) is from 0.5 to 20 cSt at 25° C.; and the averagemolecular weights in the range of 100 to 300 g/mol. Suitableisoparaffins are commercially available under the tradename ISOPAR(ExxonMobil Chemical Company, Houston Tex.), and are described in, forexample, U.S. Pat. Nos. 6,197,285, 3,818,105 and 3,439,088, and soldcommercially as ISOPAR series of isoparaffins, some of which aresummarized in Table 1.

TABLE 1 ISOPAR Series Isoparaffins distillation pour Avg. Viscosity @saturates and range point Specific 25° C. aromatics Name (° C.) (° C.)Gravity (cSt) (wt %) ISOPAR E 117-136 −63 0.72 0.85 <0.01 ISOPAR G161-176 −57 0.75 1.46 <0.01 ISOPAR H 178-188 −63 0.76 1.8 <0.01 ISOPAR K179-196 −60 0.76 1.85 <0.01 ISOPAR L 188-207 −57 0.77 1.99 <0.01 ISOPARM 223-254 −57 0.79 3.8 <0.01 ISOPAR V 272-311 −63 0.82 14.8 <0.01

In another embodiment, the isoparaffins are a mixture of branched andnormal paraffins having from 6 to 50 carbon atoms, and from 10 to 24carbon atoms in another embodiment, in the molecule. The isoparaffincomposition has a ratio of branch paraffin to n-paraffin ratio (branchparaffin:n-paraffin) ranging from 0.5:1 to 9:1 in one embodiment, andfrom 1:1 to 4:1 in another embodiment. The isoparaffins of the mixturein this embodiment contain greater than 50 wt % (by total weight of theisoparaffin composition) mono-methyl species, for example, 2-methyl,3-methyl, 4-methyl, 5-methyl or the like, with minimum formation ofbranches with substituent groups of carbon number greater than 1, suchas, for example, ethyl, propyl, butyl or the like, based on the totalweight of isoparaffins in the mixture. In one embodiment, theisoparaffins of the mixture contain greater than 70 wt % of themono-methyl species, based on the total weight of the isoparaffins inthe mixture. The isoparaffinic mixture boils within a range of from 100°C. to 350° C. in one embodiment, and within a range of from 110° C. to320° C. in another embodiment. In preparing the different grades, theparaffinic mixture is generally fractionated into cuts having narrowboiling ranges, for example, 35° C. boiling ranges. These branchparaffin/n-paraffin blends are described in, for example, U.S. Pat. No.5,906,727.

Other suitable isoparaffins are also commercial available under thetrade names SHELLSOL (by Shell), SOLTROL (by Chevron Phillips) and SASOL(by Sasol Limited). SHELLSOL is a product of the Royal Dutch/Shell Groupof Companies, for example Shellsol™ (boiling point=215-260° C.). SOLTROLis a product of Chevron Phillips Chemical Co. LP, for example SOLTROL220 (boiling point=233-280° C.). SASOL is a product of Sasol Limited(Johannesburg, South Africa), for example SASOL LPA-210, SASOL-47(boiling point=238-274° C.).

In certain embodiments of the invention the NFP having a KV of 2 cSt orless at 100° C. preferably comprises at least 50 weight %, preferably atleast 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %,preferably at least 90 wt %, preferably at least 95 wt % preferably 100wt % of C₅ to C₂₅ n-paraffins, preferably C₅ to C₂₀ n-paraffins,preferably C₅ to C₁₅ n-paraffins having less than 0.1%, preferably lessthan 0.01% aromatics. In preferred embodiments the n-paraffins have adistillation range of 30° C. or less, preferably 20° C. or less, and oran initial boiling point greater than 150° C., preferably greater than200° C., and or a specific gravity of from 0.65 to 0.85, preferably from0.70 to 0.80, preferably from 0.75 to 0.80, and or a flash point greaterthan 60° C., preferably greater than 90° C., preferably greater than100° C., preferably greater than 120° C.Suitable n-paraffins are commercially available under the tradenameNORPAR (ExxonMobil Chemical Company, Houston Tex.), and are soldcommercially as NORPAR series of n-paraffins, some of which aresummarized in Table 1a.

TABLE 1a NORPAR Series n-paraffins distillation pour Avg. Viscosity @saturates and range point Specific 25° C. aromatics Name (° C.) (° C.)Gravity) (cSt) (wt %) NORPAR 12 189-218 0.75 1.6 <0.01 NORPAR 13 222-2420.76 2.4 <0.01 NORPAR 14 241-251 0.77 2.8 <0.01 NORPAR 15 249-274 7 0.773.3 <0.01

In certain embodiments of the invention the NFP having a KV of 2 cSt orless at 100° C. preferably comprises at least 50 weight %, preferably atleast 60 wt %, preferably at least 70 wt %, preferably at least 80 wt %,preferably at least 90 wt %, preferably at least 95 wt % preferably 100wt % of a dearomaticized aliphatic hydrocarbon comprising a mixture ofnormal paraffins, isoparaffins and cycloparaffins. Typically they are amixture of C₄ to C₂₅ normal paraffins, isoparaffins and cycloparaffins,preferably C₅ to C₁₈, preferably C₅ to C₁₂. They contain very low levelsof aromatic hydrocarbons, preferably less than 0.1, preferably less than0.01 aromatics. In preferred embodiments the dearomatized aliphatichydrocarbons have a distillation range of 30° C. or less, preferably 20°C. or less, and or an initial boiling point greater than 110° C.,preferably greater than 200° C., and or a specific gravity (15.6/15.6°C.) of from 0.65 to 0.85, preferably from 0.70 to 0.85, preferably from0.75 to 0.85, preferably from 0.80 to 0.85 and or a flash point greaterthan 60° C., preferably greater than 90° C., preferably greater than100° C., preferably greater than 110° C.

Suitable dearomatized aliphatic hydrocarbons are commercially availableunder the tradename EXXSOL (ExxonMobil Chemical Company, Houston Tex.),and are sold commercially as EXXSOL series of dearomaticized aliphatichydrocarbons, some of which are summarized in Table 1b.

TABLE 1b EXXSOL Series saturates distillation pour Avg. Viscosity @ andrange point Specific 25° C. aromatics Name (° C.) (° C.) Gravity (cSt)(wt %) EXXSOL 0.63 0.3 — isopentane EXXSOL 59-62 0.66 0.5 —methylpentane naphtha EXXSOL 66-69 0.67 0.5 — hexane fluid EXXSOL 78-990.72 0.6 — DSP 75/100 EXXSOL 94-99 0.70 0.6 — heptane fluid EXXSOL 98-115 0.74 DSP 90/120 Naphtha EXXSOL 116-145 0.75 0.8 — DSP 115/145Naphtha EXXSOL D 158-178 0.77 1.2 — Naphtha EXXSOL D 40 161-202 0.79 1.40.3 EXXSOL D 60 188-210 0.80 0.4 EXXSOL D 80 208-234 0.80 2.2 0.4 EXXSOLD 95 224-238 0.80 2.1 0.7 EXXSOL D 110 249-268 0.81 3.5 0.8 EXXSOL D 130282-311 −45 0.83 6.9 1.5

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins, preferably polypropylene orpolybutene, more preferably polypropylene and one or morenon-functionalized plasticizers where the non-functionalized plasticizercomprises a polyalphaolefin comprising oligomers of C₆ to C₁₄ olefinshaving a Kinematic viscosity of 10 cSt or more at 100° C. and aviscosity index of 120 or more, preferably 130 or more.

This invention also relates to plasticized polypropylene compositionscomprising polypropylene and one or more non-functionalized plasticizerswhere the non-functionalized plasticizer comprises oligomers of C₆ toC₁₄ olefins having viscosity index of 120 or more, provided that whenthe plasticized composition comprises between 4 and 10 weight % ofpolyalphaolefin that is a hydrogenated, highly branched dimer of analpha olefin having 8-12 carbon atoms, the composition does notcomprises between 18 and 25 weight percent of a linear low densitypolyethylene having a density of 0.912 to 0.935 g/cc.

This invention also relates to plasticized polypropylene compositionscomprising polypropylene and one or more non-functionalized plasticizerswhere the non-functionalized plasticizer comprises oligomers of C₆ toC₁₄ olefins having viscosity index of 120 or more, provided that thepolyolefin does not comprises an impact copolymer of polypropylene and40-50 weight % of an ethylene propylene rubber or provided that thecomposition does not comprise a random copolymer of propylene andethylene.

In another embodiment the NFP comprises polyalphaolefins comprisingoligomers of linear olefins having 6 to 14 carbon atoms, more preferably8 to 12 carbon atoms, more preferably 10 carbon atoms having a Kinematicviscosity of 10 or more (as measured by ASTM D 445); and preferablyhaving a viscosity index (“VI”), as determined by ASTM D-2270 of 100 ormore, preferably 110 or more, more preferably 120 or more, morepreferably 130 or more, more preferably 140 or more; and/or having apour point of −5° C. or less (as determined by ASTM D 97), morepreferably −10° C. or less, more preferably −20° C. or less.

In another embodiment polyalphaolefin oligomers useful in the presentinvention comprise C₂₀ to C₁₅₀₀ paraffins, preferably C₄₀ to C₁₀₀paraffins, preferably C₅₀ to C₇₅₀ paraffins, preferably C₅₀ to C₅₀₀paraffins. The PAO oligomers are dimers, trimers, tetramers, pentamers,etc. of C₅ to C₁₄ α-olefins in one embodiment, and C₆ to C₁₂ α-olefinsin another embodiment, and C₈ to C₁₂ α-olefins in another embodiment.Suitable olefins include 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene and 1-dodecene. In one embodiment, theolefin is 1-decene, and the NFP is a mixture of dimers, trimers,tetramers and pentamers (and higher) of 1-decene. Preferred PAO's aredescribed more particularly in, for example, U.S. Pat. No. 5,171,908,and U.S. Pat. No. 5,783,531 and in SYNTHETIC LUBRICANTS ANDHIGH-PERFORMANCE FUNCTIONAL FLUIDS 1-52 (Leslie R. Rudnick & Ronald L.Shubkin, ed. Marcel Dekker, Inc. 1999).

PAO's useful in the present invention typically possess a number averagemolecular weight of from 100 to 21,000 in one embodiment, and from 200to 10,000 in another embodiment, and from 200 to 7,000 in yet anotherembodiment, and from 200 to 2,000 in yet another embodiment, and from200 to 500 in yet another embodiment. Preferred PAO's have viscositiesin the range of 0.1 to 150 cSt at 100° C., and from 0.1 to 3000 cSt at100° C. in another embodiment (ASTM 445). PAO's useful in the presentinvention typically have pour points of less than 0° C. in oneembodiment, less than −10° C. in another embodiment, and less than −20°C. in yet another embodiment, and less than −40° C. in yet anotherembodiment. Desirable PAO's are commercially available as SHF andSuperSyn PAO's (ExxonMobil Chemical Company, Houston Tex.), some ofwhich are summarized in the Table 2 below.

TABLE 2 SHF and SuperSyn Series Polyalphaolefins specific gravityViscosity @ Pour Point, PAO (15.6/15.6° C.) 100° C., cSt VI ° C. SHF-200.798 1.68 — −63 SHF-21 0.800 1.70 — −57 SHF-23 0.802 1.80 — −54 SHF-410.818 4.00 123 −57 SHF-61/63 0.826 5.80 133 −57 SHF-82/83 0.833 7.90 135−54 SHF-101 0.835 10.0 136 −54 SHF-403 0.850 40.0 152 −39 SHF-1003 0.855107 179 −33 SuperSyn 2150 0.850 150 214 −42 SuperSyn 2300 0.852 300 235−30 SuperSyn 21000 0.856 1,000 305 −18 SuperSyn 23000 0.857 3,000 388 −9

Other useful PAO's include those sold under the tradenames Synfluid™available from ChevronPhillips Chemical Co. in Pasedena Tex., Durasyn™available from BP Amoco Chemicals in London England, Nexbase™ availablefrom Fortum Oil and Gas in Finland, Synton™ available from CromptonCorporation in Middlebury Conn., USA, EMERY™ available from CognisCorporation in Ohio, USA.

In other embodiments the PAO's have a Kinematic viscosity of 10 cSt ormore at 100° C., preferably 30 cSt or more, preferably 50 cSt or more,preferably 80 cSt or more, preferably 110 or more, preferably 150 cSt ormore, preferably 200 cSt or more, preferably 500 cSt or more, preferably750 or more, preferably 1000 cSt or more, preferably 1500 cSt or more,preferably 2000 cSt or more, preferably 2500 or more. In anotherembodiment the PAO's have a kinematic viscosity at 100° C. of between 10cSt and 3000 cSt, preferably between 10 cSt and 1000 cSt, preferablybetween 10 cSt and 40 cSt.In other embodiments the PAO's have a viscosity index of 120 or more,preferably 130 or more, preferably 140 or more, preferably 150 or more,preferably 170 or more, preferably 190 or more, preferably 200 or more,preferably 250 or more, preferably 300 or more.In a particularly preferred embodiment the PAO has a kinematic viscosityof 10 cSt or more at 100° C. when the polypropylene is RB 501 F, HifaxCA12A, or ADFLEX Q 100F, as these polymers are described in WO 98/44041.

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer comprises a highpurity hydrocarbon fluid composition comprising a mixture of paraffinshaving 6 to 1500 carbon atoms, preferably 8 to 1000 carbon atoms,preferably 10 to 500 carbon atoms, preferably 12 to about 200 carbonatoms, preferably 14 to 150 carbon atoms, preferably 16 to 100 carbonatoms in the molecule. The hydrocarbon fluid composition has anisoparaffin:n-paraffin ratio ranging from about 0.5:1 to about 9:1,preferably from about 1:1 to about 4:1. The isoparaffins of the mixturecontain greater than fifty percent, 50%, mono-methyl species, e.g.,2-methyl, 3-methyl, 4-methyl, ≧5-methyl or the like, with minimumformation of branches with substituent groups of carbon number greaterthan 1, i.e., ethyl, propyl, butyl or the like, based on the totalweight of isoparaffins in the mixture. Preferably, the isoparaffins ofthe mixture contain greater than 70 percent of the mono-methyl species,based on the total weight of the isoparaffins in the mixture. Thesehydrocarbon fluids preferably have viscosities KV at 25° C. ranging from1 to 100,000 cSt, preferably 10 cSt to 2000 cSt and, optionally low pourpoints typically below −20° C., more preferably below −30° C., morepreferably ranging from about −20° C. to about −70° C. These hydrocarbonfluids preferably have viscosities KV at 40° C. ranging from 1 to 30,000cSt, preferably 10 cSt to 2000 cSt and, optionally low pour pointstypically below −20° C., more preferably below −30° C., more preferablyranging from about −20° C. to about −70° C.

This invention also relates to plasticized polyolefin compositionscomprising one or more polyolefins and one or more non-functionalizedplasticizers where the non-functionalized plasticizer comprises a linearor branched paraffinic hydrocarbon composition having:

-   1. a number average molecular weight of 500 to 21,000 g/mol;-   2. less than 10% sidechains having 4 or more carbons, preferably    less than 8 weight %, preferably less than 5 weight %, preferably    less than 3 weight %, preferably less than 2 weight %, preferably    less than 1 weight %, preferably less than 0.5 weight %, preferably    less than 0.1 weight %, preferably at less than 0.1 weight %,    preferably at 0.001 weight %;-   3. at least 1 or 2 carbon branches present at 15 weight % or more,    preferably 20 weight % or more, preferably 25 weight % or more,    preferably 30 weight % or more, preferably 35 weight % or more,    preferably 40 weight % or more, preferably 45 weight % or more,    preferably 50 weight % or more,-   4. less than 2.5 weight % cyclic paraffins, preferably less than 2    weight %, preferably less than 1 weight %, preferably less than 0.5    weight %, preferably less than 0.1 weight %, preferably at less than    0.1 weight %, preferably at 0.001 weight %. In additional    embodiments these NFP's have a kinematic viscosity 2 cSt or more at    100° C. and or a VI of 120 or more, preferably 130 or more,    preferably 140 or more, preferably 150 or more, preferably 170 or    more, preferably 190 or more, preferably 200 or more, preferably 250    or more, preferably 300 or more.

In another embodiment the NFP comprises a high purity hydrocarbon fluidcomposition which comprises a mixture of paraffins of carbon numberranging from about C₈ to C₂₀, has a molar ratio of isoparaffins:n-paraffins ranging from about 0.5:1 to about 9:1, the isoparaffins ofthe mixture contain greater than 50 percent of the mono-methyl species,based on the total weight of the isoparaffins of the mixture and whereinthe composition has pour points ranging from about −20° F. to about −70°F., and kinematic viscosities at 25° C. ranging from about 1 cSt toabout 10 cSt.

In another embodiment, the mixture of paraffins has a carbon numberranging from about C₁₀ to about C₁₆. In another embodiment, the mixturecontains greater than 70 percent of the mono-methyl species. In anotherembodiment, the mixture boils at a temperature ranging from about 320°F. to about 650° F. In another embodiment, the mixture boils within arange of from about 350° F. to about 550° F. In another embodiment, themixture comprises a mixture of paraffins of carbon number ranging fromabout C₁₀ to about C₁₆. In another embodiment, the mixture is of carbonnumbers ranging from about C₁₀-C₁₆, the mixture contains greater than 70percent of the mono-methyl species and boils within a range of fromabout 350° F. to about 550° F. In another embodiment, the mixture has amolar ratio of isoparaffins:n-paraffins ranging from about 1:1 to about4:1. In another embodiment, the mixture is derived from aFischer-Tropsch process. Such NFP's may be produced by the methodsdisclosed in U.S. Pat. No. 5,906,727.

Any of the NFP's may also be described by any number of, or anycombination of, parameters described herein. In one embodiment, any ofthe NFP's of the present invention has a pour point (ASTM D97) of fromless than 0° C. in one embodiment, and less than −5° C. in anotherembodiment, and less than −10° C. in another embodiment, less than −20°C. in yet another embodiment, less than −40° C. in yet anotherembodiment, less than −50° C. in yet another embodiment, and less than−60° C. in yet another embodiment, and greater than −120° C. in yetanother embodiment, and greater than −200° C. in yet another embodiment,wherein a desirable range may include any upper pour point limit withany lower pour point limit described herein. In one embodiment, the NFPis a paraffin or other compound having a pour point of less than −30°C., and between −30° C. and −90° C. in another embodiment, in theviscosity range of from 0.5 to 200 cSt at 40° C. (ASTM D445-97). Mostmineral oils, which typically include aromatic moieties and otherfunctional groups, have a pour point of from 10° C. to −20° C. at thesame viscosity range.

In another embodiment any NFP described herein may have a ViscosityIndex of 90 or more, preferably 95 or more, more preferably 100 or more,more preferably 105 or more, more preferably 110 or more, morepreferably 115 or more, more preferably 120 or more, more preferably 125or more, more preferably 130 or more. In another embodiment the NFP hasa VI between 90 and 400, preferably between 120 and 350.

The any NFP described herein may have a dielectric constant at 20° C. ofless than 3.0 in one embodiment, and less than 2.8 in anotherembodiment, less than 2.5 in another embodiment, and less than 2.3 inyet another embodiment, and less than 2.1 in yet another embodiment.Polyethylene and polypropylene each have a dielectric constant (1 kHz,23° C.) of at least 2.3 (CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R.Lide, ed. 82^(d) ed. CRC Press 2001).

In some embodiments, the NFP may have a kinematic viscosity (ASTMD445-97) of from 0.1 to 3000 cSt at 100° C., and from 0.5 to 1000 cSt at100° C. in another embodiment, and from 1 to 250 cSt at 100° C. inanother embodiment, and from 1 to 200 cSt at 100° C. in yet anotherembodiment, and from 10 to 500 cSt at 100° C. in yet another embodiment,wherein a desirable range may comprise any upper viscosity limit withany lower viscosity limit described herein. In other embodiments the NFPhas a kinematic viscosity of less than 2 cSt at 100° C.

In some embodiments any NFP described herein may have a specific gravity(ASTM D 4052, 15.6/15.6° C.) of less than 0.920 in one embodiment, andless than 0.910 in another embodiment, and from 0.650 to 0.900 inanother embodiment, and from 0.700 to 0.860, and from 0.750 to 0.855 inanother embodiment, and from 0.790 to 0.850 in another embodiment, andfrom 0.800 to 0.840 in yet another embodiment, wherein a desirable rangemay comprise any upper specific gravity limit with any lower specificgravity limit described herein.

In other embodiments any NFP described herein may have a boiling pointof from 100° C. to 500° C. in one embodiment, and from 200° C. to 450°C. in another embodiment, and from 250° C. to 400° C. in yet anotherembodiment. Further, the NFP preferably has a weight average molecularweight of less than 20,000 g/mol in one embodiment, and less than 10,000g/mol in yet another embodiment, and less than 5,000 g/mol in yetanother embodiment, and less than 4,000 g/mol in yet another embodiment,and less than 2,000 g/mol in yet another embodiment, and less than 500g/mol in yet another embodiment, and greater than 100 g/mol in yetanother embodiment, wherein a desirable molecular weight range can beany combination of any upper molecular weight limit with any lowermolecular weight limit described herein.

In another embodiment the NFP comprises a Group III hydrocarbonbasestock. Preferably the NFP comprises a mineral oil having a saturateslevels of 90% or more, preferably 92% or more, preferably 94% or more,preferably 96% or more, preferably 98% or more, preferably 99% or more,and sulfur contents less than 0.03%, preferably between 0.001 and 0.01%and VI is in excess of 120, preferably 130 or more.

In some embodiments, polybutenes are useful as NFP's of the presentinvention. In one embodiment of the invention, the polybutene processingoil is a low molecular weight (less than 15,000 number average molecularweight; less than 60,000 weight average molecular weight) homopolymer orcopolymer of olefin derived units having from 3 to 8 carbon atoms in oneembodiment, preferably from 4 to 6 carbon atoms in another embodiment.In yet another embodiment, the polybutene is a homopolymer or copolymerof a C₄ raffinate. An embodiment of such low molecular weight polymerstermed “polybutene” polymers is described in, for example, SYNTHETICLUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS 357-392 (Leslie R.Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999) (hereinafter“polybutene processing oil” or “polybutene”). Another preferredembodiment includes poly(n-butene) hydrocarbons. Preferredpoly(n-butenes) have less than 15,000 number average molecular weightand less than 60,000 weight average molecular weight.

In another preferred embodiment, the polybutene is a copolymer of atleast isobutylene derived units, 1-butene derived units, and 2-butenederived units. In one embodiment, the polybutene is a homopolymer,copolymer, or terpolymer of the three units, wherein the isobutylenederived units are from 40 to 100 wt % of the copolymer, the 1-butenederived units are from 0 to 40 wt % of the copolymer, and the 2-butenederived units are from 0 to 40 wt % of the copolymer. In anotherembodiment, the polybutene is a copolymer or terpolymer of the threeunits, wherein the isobutylene derived units are from 40 to 99 wt % ofthe copolymer, the 1-butene derived units are from 2 to 40 wt % of thecopolymer, and the 2-butene derived units are from 0 to 30 wt % of thecopolymer. In yet another embodiment, the polybutene is a terpolymer ofthe three units, wherein the isobutylene derived units are from 40 to 96wt % of the copolymer, the 1-butene derived units are from 2 to 40 wt %of the copolymer, and the 2-butene derived units are from 2 to 20 wt %of the copolymer. In yet another embodiment, the polybutene is ahomopolymer or copolymer of isobutylene and 1-butene, wherein theisobutylene derived units are from 65 to 100 wt % of the homopolymer orcopolymer, and the 1-butene derived units are from 0 to 35 wt % of thecopolymer.

Polybutene processing oils useful in the invention typically have anumber average molecular weight (Mn) of less than 10,000 g/mol in oneembodiment, less than 8000 g/mol in another embodiment, and less than6000 g/mol in yet another embodiment. In one embodiment, the polybuteneoil has a number average molecular weight of greater than 400 g/mol, andgreater than 700 g/mol in another embodiment, and greater than 900 g/molin yet another embodiment. A preferred embodiment can be a combinationof any lower molecular weight limit with any upper molecular weightlimit described herein. For example, in one embodiment of the polybuteneof the invention, the polybutene has a number average molecular weightof from 400 g/mol to 10,000 g/mol, and from 700 g/mol to 8000 g/mol inanother embodiment, and from 900 g/mol to 3000 g/mol in yet anotherembodiment. Useful viscosities of the polybutene processing oil rangesfrom 10 to 6000 cSt (centiStokes) at 100° C. in one embodiment, and from35 to 5000 cSt at 100° C. in another embodiment, and is greater than 35cSt at 100° C. in yet another embodiment, and greater than 100 cSt at100° C. in yet another embodiment.

Commercial examples of useful polybutenes include the PARAPOL™ Series ofprocessing oils (Infineum, Linden, N.J.), such as PARAPOL™ 450, 700,950, 1300, 2400 and 2500 and the Infineum “C” series of polybutenes,including C9945, C9900, C9907, C9913, C9922, C9925 as listed below. Thecommercially available PARAPOL™ and Infineum Series of polybuteneprocessing oils are synthetic liquid polybutenes, each individualformulation having a certain molecular weight, all formulations of whichcan be used in the composition of the invention. The molecular weightsof the PARAPOL™ oils are from 420 Mn (PARAPOL™ 450) to 2700 Mn (PARAPOL™2500) as determined by gel permeation chromatography. The MWD of thePARAPOL™ oils range from 1.8 to 3 in one embodiment, and from 2 to 2.8in another embodiment; the pour points of these polybutenes are lessthan 25° C. in one embodiment, less than 0° C. in another embodiment,and less than −10° C. in yet another embodiment, and between −80° C. and25° C. in yet another embodiment; and densities (IP 190/86 at 20° C.)range from 0.79 to 0.92 g/cm³, and from 0.81 to 0.90 g/cm³ in anotherembodiment.

Below, Tables 3 and 3a shows some of the properties of the PARAPOL™ oilsand Infineum oils useful in embodiments of the present invention,wherein the viscosity was determined as per ASTM D445-97, and the numberaverage molecular weight (M_(n)) by gel permeation chromatography.

TABLE 3 PARAPOL ™ Grades of polybutenes Grade M_(n) Viscosity @ 100° C.,cSt 450 420 10.6 700 700 78 950 950 230 1300 1300 630 2400 2350 32002500 2700 4400

TABLE 3a Infineum Grades of Polybutenes Viscosity @ 100° C., ViscosityGrade M_(n) cSt Index C9945 420 10.6 ~75 C9900 540 11.7 ~60 C9907 700 78~95 C9995 950 230 ~130 C9913 1300 630 ~175 C9922 2225 2500 ~230 C99252700 4400 ~265

Desirable NFPs for use in the present invention may thus be described byany embodiment described herein, or any combination of the embodimentsdescribed herein. For example, in one embodiment, the NFP is a C₆ toC₂₀₀ paraffin having a pour point of less than −25° C. Described anotherway, the NFP comprises an aliphatic hydrocarbon having a viscosity offrom 0.1 to 1000 cSt at 100° C. Described yet another way, the NFP isselected from n-paraffins, branched isoparaffins, and blends thereofhaving from 8 to 25 carbon atoms.

Preferred NFP's of this invention are characterized in that, whenblended with the polyolefin to form a plasticized composition, the NFPis miscible with the polyolefin as indicated by no change in the numberof peaks in the Dynamic Mechanical Thermal Analysis (DMTA) trace as inthe unplasticized polyolefin DMTA trace. Lack of miscibility isindicated by an increase in the number of peaks in DMTA trace over thosein the unplasticized polyolefin. The trace is the plot of tan-deltaversus temperature, as described below.

Preferred compositions of the present invention can be characterized inthat the glass transition temperature (T_(g)) of the compositiondecreases by at least 2° C. for every 4 wt % of NFP present in thecomposition in one embodiment; and decreases by at least 3° C. for every4 wt % of NFP present in the composition in another embodiment; anddecreases from at least 4 to 10° C. for every 4 wt % of NFP present inthe composition in yet another embodiment, while the peak melting andcrystallization temperatures of the polyolefin remain constant (within 1to 2° C.). For purpose of this invention and the claims thereto whenglass transition temperature is referred to it is the peak temperaturein the DMTA trace.

Preferred compositions of the present invention can be characterized inthat the glass transition temperature (T_(g)) of the compositiondecreases by at least 2° C. for every 1 wt % of NFP present in thecomposition in one embodiment; preferably by at least 3° C., preferablyby at least 4° C., preferably by at least 5° C., preferably by at least6° C., preferably by at least 7° C., preferably by at least 8° C.,preferably by at least 9° C., preferably by at least 10° C., preferablyby at least 11° C.; preferably while the peak melting and orcrystallization temperatures of the neat polyolefin remain within 1 to5° C. of the plasticized polyolefin, preferably within 1 to 4° C.,preferably within 1 to 3° C., preferably within 1 to 2° C.

Preferred compositions of the present invention can be characterized inthat the glass transition temperature (T_(g)) of the plasticizedcomposition is at least 2° C. lower than that of the neat polyolefin,preferably at least 4° C. lower, preferably at least 6° C. lower,preferably at least 8° C. lower, preferably at least 10° C. lower,preferably at least 15° C. lower, preferably at least 20° C. lower,preferably at least 25° C. lower, preferably at least 30° C. lower,preferably at least 35° C. lower, preferably at least 40° C. lower,preferably at least 45° C. lower.

Preferred compositions of the present invention can be characterized inthat the plasticized composition decreases less than 3%, preferably lessthan 2%, preferably less than 1% in weight when stored at 70° C. for 311hours in a dry oven as determined by ASTM D1203 using a 0.25 mm thicksheet.

Polyolefin

The NFP's described herein are blended with at least one polyolefin toprepare the plasticized compositions of this invention. Preferredpolyolefins include propylene polymers and butene polymers.

In one aspect of the invention, the polyolefin is selected frompolypropylene homopolymer, polypropylene copolymers, and blends thereof.The homopolymer may be atactic polypropylene, isotactic polypropylene,syndiotactic polypropylene and blends thereof. The copolymer can be arandom copolymer, a statistical copolymer, a block copolymer, and blendsthereof. In particular, the inventive polymer blends described hereininclude impact copolymers, elastomers and plastomers, any of which maybe physical blends or in situ blends with the polypropylene and orpolybutene. The method of making the polypropylene or polybutene is notcritical, as it can be made by slurry, solution, gas phase or othersuitable processes, and by using catalyst systems appropriate for thepolymerization of polyolefins, such as Ziegler-Natta-type catalysts,metallocene-type catalysts, other appropriate catalyst systems orcombinations thereof. In a preferred embodiment the propylene polymersand or the butene polymers are made by the catalysts, activators andprocesses described in U.S. Pat. No. 6,342,566, U.S. Pat. No. 6,384,142,WO 03/040201, WO 97/19991 and U.S. Pat. No. 5,741,563. Likewise theimpact copolymers may be prepared by the process described in U.S. Pat.No. 6,342,566, U.S. Pat. No. 6,384,142. Such catalysts are well known inthe art, and are described in, for example, ZIEGLER CATALYSTS (GerhardFink, Rolf Mülhaupt and Hans H. Brintzinger, eds., Springer-Verlag1995); Resconi et al., Selectivity in Propene Polymerization withMetallocene Catalysts, 100 CHEM. REV. 1253-1345 (2000); and I, IIMETALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).

Preferred propylene homopolymers and copolymers useful in this inventiontypically have:

-   1. an Mw of 30,000 to 2,000,000 g/mol preferably 50,000 to    1,000,000, more preferably 90,000 to 500,000, as measured by GPC as    described below in the test methods; and/or-   2. an Mw/Mn of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to    10, more preferably 1.8 to 3 as measured by GPC as described below    in the test methods; and/or-   3. a Tm (second melt) of 30 to 200° C., preferably 30 to 185° C.,    preferably 50 to 175, more preferably 60 to 170 as measured by the    DSC method described below in the test methods; and/or-   4. a crystallinity of 5 to 80%, preferably 10 to 70, more preferably    20 to 60% as measured by the DSC method described below in the test    methods; and/or-   5. a glass transition temperature (Tg) of −40° C. to 20° C.,    preferably −20° C. to 10° C., more preferably −10° C. to 5° C. as    measured by the DMTA method described below in the test methods; and    or-   6. a heat of fusion (Hf) of 180 J/g or less, preferably 20 to 150    J/g, more preferably 40 to 120 J/g as measured by the DSC method    described below in the test methods; and or-   7. a crystallization temperature (Tc) of 15 to 120° C., preferably    20 to 115° C., more preferably 25 to 110° C., preferably 60 to 145°    C., as measured by the method described below in the test methods;    and or-   8. a heat deflection temperature of 45 to 140° C., preferably 60 to    135° C., more preferably 75 to 125° C. as measured by the method    described below in the test methods; and or-   9. A Rockwell hardness (R scale) of 25 or more, preferably 40 or    more, preferably 60 or more, preferably 80 or more, preferably 100    or more, preferably from 25 to 125; and or-   10. a percent crystallinity of at least 30%, preferably at least    40%, alternatively at least 50%, as measured by the method described    below in the test methods; and or-   11. a percent amorphous content of at least 50%, alternatively at    least 60%, alternatively at least 70%, even alternatively between 50    and 95%, or 70% or less, preferably 60% or less, preferably 50% or    less as determined by subtracting the percent crystallinity from    100, and or-   12. A branching index (g′) of 0.2 to 2.0, preferably 0.5 to 1.5,    preferably 0.7 to 1.1, as measured by the method described below.

The polyolefin may be a propylene homopolymer. In one embodiment thepropylene homopolymer has a molecular weight distribution (Mw/Mn) of upto 40, preferably ranging from 1.5 to 10, and from 1.8 to 7 in anotherembodiment, and from 1.9 to 5 in yet another embodiment, and from 2.0 to4 in yet another embodiment. In another embodiment the propylenehomopolymer has a Gardner impact strength, tested on 0.125 inch disk at23° C., that may range from 20 in-lb to 1000 in-lb in one embodiment,and from 30 in-lb to 500 in-lb in another embodiment, and from 40 in-lbto 400 in-lb in yet another embodiment. In yet another embodiment, the1% secant flexural modulus may range from 100 MPa to 2300 MPa, and from200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPain yet another embodiment, wherein a desirable polyolefin may exhibitany combination of any upper flexural modulus limit with any lowerflexural modulus limit. The melt flow rate (MFR) (ASTM D 1238, 230° C.,2.16 kg) of preferred propylene polymers range from 0.1 dg/min to 2500dg/min in one embodiment, and from 0.3 to 500 dg/min in anotherembodiment.

The polypropylene homopolymer or propylene copolymer useful in thepresent invention may have some level of isotacticity. Thus, in oneembodiment, a polyolefin comprising isotactic polypropylene is a usefulpolymer in the invention of this patent, and similarly, highly isotacticpolypropylene is useful in another embodiment. As used herein,“isotactic” is defined as having at least 10% isotactic pentadsaccording to analysis by ¹³C-NMR as described in the test methods below.As used herein, “highly isotactic” is defined as having at least 60%isotactic pentads according to analysis by ¹³C-NMR. In a desirableembodiment, a polypropylene homopolymer having at least 85% isotacticityis the polyolefin, and at least 90% isotacticity in yet anotherembodiment.

In another desirable embodiment, a polypropylene homopolymer having atleast 85% syndiotacticity is the polyolefin, and at least 90%syndiotacticity in yet another embodiment. As used herein,“syndiotactic” is defined as having at least 10% syndiotactic pentadsaccording to analysis by ¹³C-NMR as described in the test methods below.As used herein, “highly syndiotactic” is defined as having at least 60%syndiotactic pentads according to analysis by ¹³C-NMR.

In another embodiment the propylene homoploymer may be isotactic, highlyisotactic, syndiotactic, highly syndiotactic or atactic. Atacticpolypropylene is defined to be less than 10% isotactic or syndiotacticpentads. Preferred atactic polypropylenes typically have an Mw of 20,000up to 1,000,000.

Preferred propylene polymers that are useful in this invention includethose sold under the tradenames ACHIEVE™ and ESCORENE™ by ExxonMobilChemical Company in Houston Tex.

In another embodiment of the invention, the polyolefin is a propylenecopolymer, either random, or block, of propylene derived units and unitsselected from ethylene and C₄ to C₂₀ α-olefin derived units, typicallyfrom ethylene and C₄ to C₁₀ α-olefin derived units in anotherembodiment. The ethylene or C₄ to C₂₀ α-olefin derived units are presentfrom 0.1 wt % to 50 wt % of the copolymer in one embodiment, and from0.5 to 30 wt % in another embodiment, and from 1 to 15 wt % in yetanother embodiment, and from 0.1 to 5 wt % in yet another embodiment,wherein a desirable copolymer comprises ethylene and C₄ to C₂₀ α-olefinderived units in any combination of any upper wt % limit with any lowerwt % limit described herein. The propylene copolymer will have a weightaverage molecular weight of from greater than 8,000 g/mol in oneembodiment, and greater than 10,000 g/mol in another embodiment, andgreater than 12,000 g/mol in yet another embodiment, and greater than20,000 g/mol in yet another embodiment, and less than 1,000,000 g/mol inyet another embodiment, and less than 800,000 in yet another embodiment,wherein a desirable copolymer may comprise any upper molecular weightlimit with any lower molecular weight limit described herein.

Particularly desirable propylene copolymers have a molecular weightdistribution (Mw/Mn) ranging from 1.5 to 10, and from 1.6 to 7 inanother embodiment, and from 1.7 to 5 in yet another embodiment, andfrom 1.8 to 4 in yet another embodiment. The Gardner impact strength,tested on 0.125 inch disk at 23° C., of the propylene copolymer mayrange from 20 in-lb to 1000 in-lb in one embodiment, and from 30 in-lbto 500 in-lb in another embodiment, and from 40 in-lb to 400 in-lb inyet another embodiment. In yet another embodiment, the 1% secantflexural modulus of the propylene copolymer ranges from 100 MPa to 2300MPa, and from 200 MPa to 2100 MPa in another embodiment, and from 300MPa to 2000 MPa in yet another embodiment, wherein a desirablepolyolefin may exhibit any combination of any upper flexural moduluslimit with any lower flexural modulus limit. The melt flow rate (MFR)(ASTM D 1238, 230° C., 2.16 kg) of propylene copolymer ranges from 0.1dg/min to 2500 dg/min in one embodiment, and from 0.3 to 500 dg/min inanother embodiment.

In another embodiment the polyolefin may be a propylene copolymercomprising propylene and one or more other monomers selected from thegroup consisting of ethylene and C₄ to C₂₀ linear, branched or cyclicmonomers, and in some embodiments is a C₄ to C₁₂ linear or branchedalpha-olefin, preferably butene, pentene, hexene, heptene, octene,nonene, decene, dodecene, 4-methyl-pentene-1,3-methylpentene-1,3,5,5-trimethyl-hexene-1, and the like. The monomers may bepresent at up to 50 weight %, preferably from 0 to 40 weight %, morepreferably from 0.5 to 30 weight %, more preferably from 2 to 30 weight%, more preferably from 5 to 20 weight %.

In a preferred embodiment the butene homopolymers and copolymers usefulin this invention typically have:

-   1. an Mw of 30,000 to 2,000,000 g/mol preferably 50,000 to    1,000,000, more preferably 90,000 to 500,000, as measured by GPC as    described below in the test methods; and/or-   2. an Mw/Mn of 1 to 40, preferably 1.6 to 20, more preferably 1.8 to    10, more preferably 1.8 to 3 as measured by GPC as described below    in the test methods; and/or-   3. a Tm (second melt) of 30 to 150° C., preferably 30 to 145° C.,    preferably 50 to 135, as measured by the DSC method described below    in the test methods; and/or-   4. a crystallinity of 5 to 80%, preferably 10 to 70, more preferably    20 to 60% as measured by the DSC method described below in the test    methods; and/or-   5. a glass transition temperature (Tg) of −50° C. to 0° C. as    measured by the DMTA method described below in the test methods; and    or-   6. a heat of fusion (Hf) of 180 J/g or less, preferably 20 to 150    J/g, more preferably 40 to 120 J/g as measured by the DSC method    described below in the test methods; and or-   7. a crystallization temperature (Tc) of 10 to 130° C., preferably    20 to 115° C., more preferably 25 to 110° C., preferably 60 to 145°    C., as measured by the method described below in the test methods;    and or-   8. a percent amorphous content of at least 50%, alternatively at    least 60%, alternatively at least 70%, even alternatively between 50    and 95%, or 70% or less, preferably 60% or less, preferably 50% or    less as determined by subtracting the percent crystallinity from    100, and or-   9. A branching index (g′) of 0.2 to 2.0, preferably 0.5 to 1.5,    preferably 0.7 to 1.1, as measured by the method described below.

Preferred linear alpha-olefins useful as comonomers for the propylenecopolymers useful in this invention include C₃ to C₈ alpha-olefins, morepreferably 1-butene, 1-hexene, and 1-octene, even more preferably1-butene. Preferred linear alpha-olefins useful as comonomers for thebutene copolymers useful in this invention include C₃ to C₈alpha-olefins, more preferably propylene, 1-hexene, and 1-octene, evenmore preferably propylene. Preferred branched alpha-olefins include4-methyl-1-pentene, 3-methyl-1-pentene, and 3,5,5-trimethyl-1-hexene,5-ethyl-1-nonene. Preferred aromatic-group-containing monomers containup to 30 carbon atoms. Suitable aromatic-group-containing monomerscomprise at least one aromatic structure, preferably from one to three,more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety. Thearomatic-group-containing monomer further comprises at least onepolymerizable double bond such that after polymerization, the aromaticstructure will be pendant from the polymer backbone. The aromatic-groupcontaining monomer may further be substituted with one or morehydrocarbyl groups including but not limited to C1 to C10 alkyl groups.Additionally two adjacent substitutions may be joined to form a ringstructure. Preferred aromatic-group-containing monomers contain at leastone aromatic structure appended to a polymerizable olefinic moiety.Particularly preferred aromatic monomers include styrene,alpha-methylstyrene, para-alkylstyrenes, vinyltoluenes,vinylnaphthalene, allyl benzene, and indene, especially styrene,paramethyl styrene, 4-phenyl-1-butene and allyl benzene.

Non aromatic cyclic group containing monomers are also preferred. Thesemonomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclicgroup containing monomers preferably have at least one polymerizableolefinic group that is either pendant on the cyclic structure or is partof the cyclic structure. The cyclic structure may also be furthersubstituted by one or more hydrocarbyl groups such as, but not limitedto, C1 to C10 alkyl groups. Preferred non-aromatic cyclic groupcontaining monomers include vinylcyclohexane, vinylcyclohexene,vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene,cyclohexene, cyclobutene, vinyladamantane and the like.

Preferred diolefin monomers useful in this invention include anyhydrocarbon structure, preferably C4 to C30, having at least twounsaturated bonds, wherein at least two of the unsaturated bonds arereadily incorporated into a polymer by either a stereospecific or anon-stereospecific catalyst(s). It is further preferred that thediolefin monomers be selected from alpha, omega-diene monomers (i.e.di-vinyl monomers). More preferably, the diolefin monomers are lineardi-vinyl monomers, most preferably those containing from 4 to 30 carbonatoms. Examples of preferred dienes include butadiene, pentadiene,hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene,dodecadiene, tridecadiene, tetradecadiene, pentadecadiene,hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene,heneicosadiene, docosadiene, tricosadiene, tetracosadiene,pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene,nonacosadiene, triacontadiene, particularly preferred dienes include1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, and low molecular weight polybutadienes (Mw lessthan 1000 g/mol). Preferred cyclic dienes include cyclopentadiene,vinylnorbornene, norbornadiene, ethylidene norbornene, divinylbenzene,dicyclopentadiene or higher ring containing diolefins with or withoutsubstituents at various ring positions.

In a preferred embodiment one or more dienes are present in the polymerproduced herein at up to 10 weight %, preferably at 0.00001 to 1.0weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003to 0.2 weight %, based upon the total weight of the composition. In someembodiments 500 ppm or less of diene is added to the polymerization,preferably 400 ppm or less, preferably or 300 ppm or less. In otherembodiments at least 50 ppm of diene is added to the polymerization, or100 ppm or more, or 150 ppm or more.

In yet another embodiment, the Gardner impact strength, tested on 0.125inch disk at 23° C., of the butene copolymer ranges from 20 in-lb to1000 in-lb, and from 30 in-lb to 500 in-lb in another embodiment, andfrom 40 in-lb to 400 in-lb in yet another embodiment. Further, thebutene copolymer may possess a 1% secant flexural modulus ranging from100 MPa to 2300 MPa, and from 200 MPa to 2100 MPa in another embodiment,and from 300 MPa to 2000 MPa in yet another embodiment, wherein adesirable polyolefin may exhibit any combination of any upper flexuralmodulus limit with any lower flexural modulus limit. The melt flow rate(MFR) (ASTM D 1238, 230° C.) of desirable copolymers ranges from 0.1dg/min to 2500 dg/min in one embodiment, and from 0.1 to 500 dg/min inanother embodiment.

In another embodiment the propylene copolymer is a random copolymer,also known as an “RCP,” comprising propylene and up to 20 mole % ofethylene or a C₄ to C₂₀ olefin, preferably up to 20 mole % ethylene.

In another embodiment, the polyolefin may be an impact copolymer (ICP)or block copolymer. Propylene impact copolymers are commonly used in avariety of applications where strength and impact resistance are desiredsuch as molded and extruded automobile parts, household appliances,luggage and furniture. Propylene homopolymers alone are often unsuitablefor such applications because they are too brittle and have low impactresistance particularly at low temperature, whereas propylene impactcopolymers are specifically engineered for applications such as these.

A typical propylene impact copolymer contains at least two phases orcomponents, e.g., a homopolymer component and a copolymer component. Theimpact copolymer may also comprise three phases such as a PP/EP/PEcombination with the PP continuous and a dispersed phase with EP outsideand PE inside the dispersed phase particles. These components areusually produced in a sequential polymerization process wherein thehomopolymer produced in a first reactor is transferred to a secondreactor where copolymer is produced and incorporated within the matrixof the homopolymer component. The copolymer component has rubberycharacteristics and provides the desired impact resistance, whereas thehomopolymer component provides overall stiffness.

Another important feature of ICP's is the amount of amorphouspolypropylene they contain. The ICP's of this invention arecharacterized as having low amorphous polypropylene, preferably lessthan 3% by weight, more preferably less than 2% by weight, even morepreferably less than 1% by weight and most preferably there is nomeasurable amorphous polypropylene. Percent amorphous polypropylene isdetermined by the method described below in the test methods.

Preferred impact copolymers may be a reactor blend (in situ blend) or apost reactor (ex-situ) blend. In one embodiment, a suitable impactcopolymer comprises from 40% to 95% by weight Component A and from 5% to60% by weight Component B based on the total weight of the impactcopolymer; wherein Component A comprises propylene homopolymer orcopolymer, the copolymer comprising 10% or less by weight ethylene,butene, hexene or octene comonomer; and wherein Component B comprisespropylene copolymer, wherein the copolymer comprises from 5% to 70% byweight ethylene, butene, hexene and/or octene comonomer, and from about95% to about 30% by weight propylene. In one embodiment of the impactcopolymer, Component B consists essentially of propylene and from about30% to about 65% by weight ethylene. In another embodiment, Component Bcomprises ethylene-propylene copolymers, ethylene-propylene-dieneterpolymers, ethylene-acrylate copolymers, ethylene-vinyl acetate,styrene-butadiene copolymers, ethylene-acrylic ester copolymers,polybutadiene, polyisoprene, natural rubber, isobutylene, hydrocarbonresin (the hydrocarbon resin being characterized by a molecular weightless than 5000, a T_(g) of about 50 to 100° C. and a softening point,Ring and Ball, as measured by ASTM E-28, of less than about 140° C.),rosin ester, and mixtures thereof. In another embodiment, Component Bhas a molecular weight distribution of less than 3.5. In yet anotherembodiment, Component B has a weight average molecular weight of atleast 20,000. A useful impact copolymer is disclosed in, for example,U.S. Pat. No. 6,342,566 and U.S. Pat. No. 6,384,142.

Component B is most preferably a copolymer consisting essentially ofpropylene and ethylene although other propylene copolymers, ethylenecopolymers or terpolymers may be suitable depending on the particularproduct properties desired. For example, propylene/butene, hexene oroctene copolymers, and ethylene/butene, hexene or octene copolymers maybe used, and propylene/ethylene/hexene-1 terpolymers may be used. In apreferred embodiment though, Component B is a copolymer comprising atleast 40% by weight propylene, more preferably from about 80% by weightto about 30% by weight propylene, even more preferably from about 70% byweight to about 35% by weight propylene. The comonomer content ofComponent B is preferably in the range of from about 20% to about 70% byweight comonomer, more preferably from about 30% to about 65% by weightcomonomer, even more preferably from about 35% to about 60% by weightcomonomer. Most preferably Component B consists essentially of propyleneand from about 20% to about 70% ethylene, more preferably from about 30%to about 65% ethylene, and most preferably from about 35% to about 60%ethylene.

For other Component B copolymers, the comonomer contents will need to beadjusted depending on the specific properties desired. For example, forethylene/hexene copolymers, Component B should contain at least 17% byweight hexene and at least 83% by weight ethylene.

Component B, preferably has a narrow molecular weight distribution Mw/Mn(“MWD”), i.e., lower than 5.0, preferably lower than 4.0, morepreferably lower than 3.5, even more preferably lower than 3.0 and mostpreferably 2.5 or lower. These molecular weight distributions should beobtained in the absence of visbreaking or peroxide or other post reactortreatment molecular weight tailoring. Component B preferably has aweight average molecular weight (Mw as determined by GPC) of at least100,000, preferably at least 150,000, and most preferably at least200,000.

Component B preferably has an intrinsic viscosity greater than 1.00dl/g, more preferably greater than 1.50 dl/g and most preferably greaterthan 2.00 dl/g. The term “intrinsic viscosity” or “IV” is usedconventionally herein to mean the viscosity of a solution of polymersuch as Component B in a given solvent at a given temperature, when thepolymer composition is at infinite dilution. According to the ASTMstandard test method D 1601-78, IV measurement involves a standardcapillary viscosity measuring device, in which the viscosity of a seriesof concentrations of the polymer in the solvent at the given temperatureare determined. For Component B, decalin is a suitable solvent and atypical temperature is 135° C. From the values of the viscosity ofsolutions of varying concentrations, the “value” at infinite dilutioncan be determined by extrapolation.

Component B preferably has a composition distribution breadth index(CDBI) of greater than 60%, more preferably greater than 65%, even morepreferably greater than 70%, even more preferably greater than 75%,still more preferably greater than 80%, and most preferably greater than85%. CDBI defines the compositional variation among polymer chains interms of ethylene (or other comonomer) content of the copolymer as awhole. A measure of composition distribution is the “CompositionDistribution Breadth Index” (“CDBI”) as defined in U.S. Pat. No.5,382,630 which is hereby incorporate by reference. CDBI is defined asthe weight percent of the copolymer molecules having a comonomer contentwithin 50% of the median total molar comonomer content. The CDBI of acopolymer is readily determined utilizing well known techniques forisolating individual fractions of a sample of the copolymer. One suchtechnique is Temperature Rising Elution Fraction (TREF), as described inWild, et al., J. Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982) andU.S. Pat. No. 5,008,204, which are incorporated herein by reference.

Component B of the ICP's preferably has low crystallinity, preferablyless than 10% by weight of a crystalline portion, more preferably lessthan 5% by weight of a crystalline portion. Where there is a crystallineportion of Component B, its composition is preferably the same as or atleast similar to (within 15% by weight) the remainder of Component B interms of overall comonomer weight percent.

The preferred melt flow rate (“MFR”) of these ICP's depends on thedesired end use but is typically in the range of from about 0.2 dg/minto about 200 dg/min, more preferably from about 5 dg/min to about 100dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min areobtainable. The ICP preferably has a melting point (Tm) of at least 145°C., preferably at least 150° C., more preferably at least 152° C., andmost preferably at least 155° C.

The ICP's comprise from about 40% to about 95% by weight Component A andfrom about 5% to about 60% by weight Component B, preferably from about50% to about 95% by weight Component A and from about 5% to about 50%Component B, even more preferably from about 60% to about 90% by weightComponent A and from about 10% to about 40% by weight Component B. Inthe most preferred embodiment, the ICP consists essentially ofComponents A and B. The overall comonomer (preferably ethylene) contentof the total ICP is preferably in the range of from about 2% to about30% by weight, preferably from about 5% to about 25% by weight, evenmore preferably from about 5% to about 20% by weight, still morepreferably from about 5% to about 15% by weight comonomer.

In another embodiment a preferred impact copolymer composition isprepared by selecting Component A and Component B such that theirrefractive indices (as measured by ASTM D 542-00) are within 20% of eachother, preferably within 15%, preferably 10, even more preferably within5% of each other. This selection produces impact copolymers withoutstanding clarity. In another embodiment a preferred impact copolymercomposition is prepared by selecting a blend of Component A and an NFPand a blend of Component B and an NFP such that refractive indices ofthe blends (as measured by ASTM D 542-00) are within 20% of each other,preferably within 15%, preferably 10, even more preferably within 5% ofeach other.

In yet another embodiment, the Gardner impact strength, tested on 0.125inch disk at −29° C., of the propylene impact copolymer ranges from 20in-lb to 1000 in-lb, and from 30 in-lb to 500 in-lb in anotherembodiment, and from 40 in-lb to 400 in-lb in yet another embodiment.Further, the 1% secant flexural modulus of the propylene impactcopolymer may range from 100 MPa to 2300 MPa in one embodiment, and from200 MPa to 2100 MPa in another embodiment, and from 300 MPa to 2000 MPain yet another embodiment, wherein a desirable polyolefin may exhibitany combination of any upper flexural modulus limit with any lowerflexural modulus limit. The melt flow rate (MFR) (ASTM D 1238, 230° C.,2.16 kg) of desirable homopolymers ranges from 0.1 dg/min to 2500 dg/minin one embodiment, and from 0.3 to 500 dg/min in another embodiment.

Another suitable polyolefin comprises a blend of a polypropylenehomopolymer or propylene copolymer with a plastomer. The plastomers thatare useful in the present invention may be described as polyolefincopolymers having a density of from 0.85 to 0.915 g/cm³ ASTM D 4703Method B and ASTM D 1505—the first of these is compression molding at acooling rate of 15° C./min and the second is the Gradient Density Columnmethod for density determination and a melt index (MI) between 0.10 and30 dg/min (ASTM D 1238; 190° C., 2.1 kg). In one embodiment, the usefulplastomer is a copolymer of ethylene derived units and at least one ofC₃ to C₁₀ α-olefin derived units, the copolymer having a density lessthan 0.915 g/cm³. The amount of comonomer (C₃ to C₁₀ α-olefin derivedunits) present in the plastomer ranges from 2 wt % to 35 wt % in oneembodiment, and from 5 wt % to 30 wt % in another embodiment, and from15 wt % to 25 wt % in yet another embodiment, and from 20 wt % to 30 wt% in yet another embodiment.

The plastomer useful in the invention has a melt index (MI) of between0.10 and 20 dg/min in one embodiment, and from 0.2 to 10 dg/min inanother embodiment, and from 0.3 to 8 dg/min in yet another embodiment.The average molecular weight of useful plastomers ranges from 10,000 to800,000 in one embodiment, and from 20,000 to 700,000 in anotherembodiment. The 1% secant flexural modulus (ASTM D 790) of usefulplastomers ranges from 10 MPa to 150 MPa in one embodiment, and from 20MPa to 100 MPa in another embodiment. Further, the plastomer that isuseful in compositions of the present invention has a meltingtemperature (T_(m)) of from 30 to 80° C. (first melt peak) and from 50to 125° C. (second melt peak) in one embodiment, and from 40 to 70° C.(first melt peak) and from 50 to 100° C. (second melt peak) in anotherembodiment.

Plastomers useful in the present invention are metallocene catalyzedcopolymers of ethylene derived units and higher α-olefin derived unitssuch as propylene, 1-butene, 1-hexene and 1-octene, and which containenough of one or more of these comonomer units to yield a densitybetween 0.860 and 0.900 g/cm³ in one embodiment. The molecular weightdistribution (Mw/Mn) of desirable plastomers ranges from 1.5 to 5 in oneembodiment, and from 2.0 to 4 in another embodiment. Examples of acommercially available plastomers are EXACT 4150, a copolymer ofethylene and 1-hexene, the 1-hexene derived units making up from 18 to22 wt % of the plastomer and having a density of 0.895 g/cm³ and MI of3.5 dg/min (ExxonMobil Chemical Company, Houston, Tex.); and EXACT 8201,a copolymer of ethylene and 1-octene, the 1-octene derived units makingup from 26 to 30 wt % of the plastomer, and having a density of 0.882g/cm³ and MI of 1.0 dg/min (ExxonMobil Chemical Company, Houston, Tex.).

In another embodiment polymers that are useful in this invention includehomopolymers and random copolymers of propylene having a heat of fusionas determined by Differential Scanning Calorimetry (DSC) of less than 50J/g, a melt index (MI) of less than 20 dg/min and or an MFR of 20 dg/minor less, and contains stereoregular propylene crystallinity preferablyisotactic stereoregular propylene crystallinity. In another embodimentthe polymer is a random copolymer of propylene and at least onecomonomer selected from ethylene, C₄-C₁₂ α-olefins, and combinationsthereof. Preferably the random copolymers of propylene comprises from 2wt % to 25 wt % polymerized ethylene units, based on the total weight ofthe polymer; has a narrow composition distribution; has a melting point(Tm) of from 25° C. to 120° C., or from 35° C. to 80° C.; has a heat offusion within the range having an upper limit of 50 J/g or 25 J/g and alower limit of 1 J/g or 3 J/g; has a molecular weight distribution Mw/Mnof from 1.8 to 4.5; and has a melt index (MI) of less than 20 dg/min, orless than 15 dg/min. The intermolecular composition distribution of thecopolymer is determined by thermal fractionation in a solvent. A typicalsolvent is a saturated hydrocarbon such as hexane or heptane. Thethermal fractionation procedure is described below. Typically,approximately 75% by weight, preferably 85% by weight, of the copolymeris isolated as one or two adjacent, soluble fractions with the balanceof the copolymer in immediately preceding or succeeding fractions. Eachof these fractions has a composition (wt % comonomer such as ethylene orother α-olefin) with a difference of no greater than 20% (relative),preferably 10% (relative), of the average weight % comonomer of thecopolymer. The copolymer has a narrow composition distribution if itmeets the fractionation test described above.

A particularly preferred polymer useful in the present invention is anelastic polymer with a moderate level of crystallinity due tostereoregular propylene sequences. The polymer can be: (A) a propylenehomopolymer in which the stereoregularity is disrupted in some mannersuch as by regio-inversions; (B) a random propylene copolymer in whichthe propylene stereoregularity is disrupted at least in part bycomonomers; or (C) a combination of (A) and (B).

In one embodiment, the polymer further includes a non-conjugated dienemonomer to aid in vulcanization and other chemical modification of theblend composition. The amount of diene present in the polymer ispreferably less than 10% by weight, and more preferably less than 5% byweight. The diene may be any non-conjugated diene which is commonly usedfor the vulcanization of ethylene propylene rubbers including, but notlimited to, ethylidene norbornene, vinyl norbornene, anddicyclopentadiene.

In one embodiment, the polymer is a random copolymer of propylene and atleast one comonomer selected from ethylene, C₄-C₁₂ α-olefins, andcombinations thereof. In a particular aspect of this embodiment, thecopolymer includes ethylene-derived units in an amount ranging from alower limit of 2%, 5%, 6%, 8%, or 10% by weight to an upper limit of20%, 25%, or 28% by weight. This embodiment will also includepropylene-derived units present in the copolymer in an amount rangingfrom a lower limit of 72%, 75%, or 80% by weight to an upper limit of98%, 95%, 94%, 92%, or 90% by weight. These percentages by weight arebased on the total weight of the propylene and ethylene-derived units;i.e., based on the sum of weight percent propylene-derived units andweight percent ethylene-derived units being 100%. The ethylenecomposition of a polymer can be measured as follows. A thin homogeneousfilm is pressed at a temperature of about 150° C. or greater, thenmounted on a Perkin Elmer PE 1760 infrared spectrophotometer. A fullspectrum of the sample from 600 cm⁻¹ to 4000 cm⁻¹ is recorded and themonomer weight percent of ethylene can be calculated according to thefollowing equation: Ethylene wt %=82.585−111.987X+30.045 X², wherein Xis the ratio of the peak height at 1155 cm¹ and peak height at either722 cm⁻¹ or 732 cm⁻¹, whichever is higher. The concentrations of othermonomers in the polymer can also be measured using this method.

Comonomer content of discrete molecular weight ranges can be measured byFourier Transform Infrared Spectroscopy (FTIR) in conjunction withsamples collected by GPC. One such method is described in Wheeler andWillis, Applied Spectroscopy, 1993, vol. 47, pp. 1128-1130. Differentbut similar methods are equally functional for this purpose and wellknown to those skilled in the art.

Comonomer content and sequence distribution of the polymers can bemeasured by ¹³C nuclear magnetic resonance (¹³C NMR), and such method iswell known to those skilled in the art.

In one embodiment, the polymer is a random propylene copolymer having anarrow composition distribution. In another embodiment, the polymer is arandom propylene copolymer having a narrow composition distribution anda melting point of from 25° C. to 110° C. The copolymer is described asrandom because for a polymer comprising propylene, comonomer, andoptionally diene, the number and distribution of comonomer residues isconsistent with the random statistical polymerization of the monomers.In stereoblock structures, the number of block monomer residues of anyone kind adjacent to one another is greater than predicted from astatistical distribution in random copolymers with a similarcomposition. Historical ethylene-propylene copolymers with stereoblockstructure have a distribution of ethylene residues consistent with theseblocky structures rather than a random statistical distribution of themonomer residues in the polymer. The intramolecular compositiondistribution (i.e., randomness) of the copolymer may be determined by¹³C NMR, which locates the comonomer residues in relation to theneighbouring propylene residues. The intermolecular compositiondistribution of the copolymer is determined by thermal fractionation ina solvent. A typical solvent is a saturated hydrocarbon such as hexaneor heptane. Typically, approximately 75% by weight, preferably 85% byweight, of the copolymer is isolated as one or two adjacent, solublefractions with the balance of the copolymer in immediately preceding orsucceeding fractions. Each of these fractions has a composition (wt %comonomer such as ethylene or other α-olefin) with a difference of nogreater than 20% (relative), preferably 10% (relative), of the averageweight % comonomer of the copolymer. The copolymer has a narrowcomposition distribution if it meets the fractionation test describedabove. To produce a copolymer having the desired randomness and narrowcomposition, it is beneficial if (1) a single sited metallocene catalystis used which allows only a single statistical mode of addition of thefirst and second monomer sequences and (2) the copolymer is well-mixedin a continuous flow stirred tank polymerization reactor which allowsonly a single polymerization environment for substantially all of thepolymer chains of the copolymer.

The crystallinity of the polymers may be expressed in terms of heat offusion. Embodiments of the present invention include polymers having aheat of fusion, as determined by DSC, ranging from a lower limit of 1.0J/g, or 3.0 J/g, to an upper limit of 50 J/g, or 10 J/g. Without wishingto be bound by theory, it is believed that the polymers of embodimentsof the present invention have generally isotactic crystallizablepropylene sequences, and the above heats of fusion are believed to bedue to the melting of these crystalline segments.

The crystallinity of the polymer may also be expressed in terms ofcrystallinity percent. The thermal energy for the highest order ofpolypropylene is estimated at 207 J/g. That is, 100% crystallinity isequal to 207 J/g. Preferably, the polymer has a polypropylenecrystallinity within the range having an upper limit of 65%, 40%, 30%,25%, or 20%, and a lower limit of 1%, 3%, 5%, 7%, or 8%.

The level of crystallinity is also reflected in the melting point. Theterm “melting point,” as used herein, is the highest peak highestmeaning the largest amount of polymer being reflected as opposed to thepeak occurring at the highest temperature among principal and secondarymelting peaks as determined by DSC, discussed above. In one embodimentof the present invention, the polymer has a single melting point.Typically, a sample of propylene copolymer will show secondary meltingpeaks adjacent to the principal peak, which are considered together as asingle melting point. The highest of these peaks is considered themelting point. The polymer preferably has a melting point by DSC rangingfrom an upper limit of 110° C., 105° C., 90° C., 80° C., or 70° C., to alower limit of 0° C., 20° C., 25° C., 30° C., 35° C., 40° C., or 45° C.

Such polymers used in the invention have a weight average molecularweight (Mw) within the range having an upper limit of 5,000,000 g/mol,1,000,000 g/mol, or 500,000 g/mol, and a lower limit of 10,000 g/mol,20,000 g/mol, or 80,000 g/mol, and a molecular weight distribution Mw/Mn(MWD), sometimes referred to as a “polydispersity index” (PDI), rangingfrom a lower limit of 1.5, 1.8, or 2.0 to an upper limit of 40, 20, 10,5, or 4.5. In one embodiment, the polymer has a Mooney viscosity,ML(1+4) @ 125° C., of 100 or less, 75 or less, 60 or less, or 30 orless. Mooney viscosity, as used herein, can be measured as ML(1+4) @125° C. according to ASTM D1646, unless otherwise specified.

The polymers used in embodiments of the present invention can have atacticity index (m/r) ranging from a lower limit of 4 or 6 to an upperlimit of 8, 10, or 12. The tacticity index, expressed herein as “m/r”,is determined by ¹³C nuclear magnetic resonance (NMR). The tacticityindex m/r is calculated as defined in H. N. Cheng, Macromolecules, 17,1950 (1984). The designation “m” or “r” describes the stereochemistry ofpairs of contiguous propylene groups, “m” referring to meso and “r” toracemic. An m/r ratio of 0 to less than 1.0 generally describes asyndiotactic polymer, and an m/r ratio of 1.0 an atactic material, andan m/r ratio of greater than 1.0 an isotactic material. An isotacticmaterial theoretically may have a ratio approaching infinity, and manyby-product atactic polymers have sufficient isotactic content to resultin ratios of greater than 50.

In one embodiment, the polymer has isotactic stereoregular propylenecrystallinity. The term “stereoregular” as used herein means that thepredominant number, i.e. greater than 80%, of the propylene residues inthe polypropylene or in the polypropylene continuous phase of a blend,such as impact copolymer exclusive of any other monomer such asethylene, has the same 1,2 insertion and the stereochemical orientationof the pendant methyl groups is the same, either meso or racemic.

An ancillary procedure for the description of the tacticity of thepropylene units of embodiments of the current invention is the use oftriad tacticity. The triad tacticity of a polymer is the relativetacticity of a sequence of three adjacent propylene units, a chainconsisting of head to tail bonds, expressed as a binary combination of mand r sequences. It is usually expressed for copolymers of the presentinvention as the ratio of the number of units of the specified tacticityto all of the propylene triads in the copolymer.

The triad tacticity (mm fraction) of a propylene copolymer can bedetermined from a ¹³C NMR spectrum of the propylene copolymer and thefollowing formula:

${{mm}\mspace{14mu} {Fraction}} = \frac{{PPP}({mm})}{{{PPP}({mm})} + {{PPP}({mr})} + {{PPP}({rr})}}$

where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from themethyl groups of the second units in the following three propylene unitchains consisting of head-to-tail bonds:

The ¹³C NMR spectrum of the propylene copolymer is measured as describedin U.S. Pat. No. 5,504,172. The spectrum relating to the methyl carbonregion (19-23 parts per million (ppm)) can be divided into a firstregion (21.2-21.9 ppm), a second region (20.3-21.0 ppm) and a thirdregion (19.5-20.3 ppm). Each peak in the spectrum was assigned withreference to an article in the journal Polymer, Volume 30 (1989), page1350. In the first region, the methyl group of the second unit in thethree propylene unit chain represented by PPP (mm) resonates. In thesecond region, the methyl group of the second unit in the threepropylene unit chain represented by PPP (mr) resonates, and the methylgroup (PPE-methyl group) of a propylene unit whose adjacent units are apropylene unit and an ethylene unit resonates (in the vicinity of 20.7ppm). In the third region, the methyl group of the second unit in thethree propylene unit chain represented by PPP (rr) resonates, and themethyl group (EPE-methyl group) of a propylene unit whose adjacent unitsare ethylene units resonates (in the vicinity of 19.8 ppm).

The calculation of the triad tacticity is outlined in the techniquesshown in U.S. Pat. No. 5,504,172. Subtraction of the peak areas for theerror in propylene insertions (both 2,1 and 1,3) from peak areas fromthe total peak areas of the second region and the third region, the peakareas based on the 3 propylene units-chains (PPP(mr) and PPP(rr))consisting of head-to-tail bonds can be obtained. Thus, the peak areasof PPP(mm), PPP(mr) and PPP(rr) can be evaluated, and hence the triadtacticity of the propylene unit chain consisting of head-to-tail bondscan be determined.

The polymers of embodiments of the present invention have a triadtacticity of three propylene units, as measured by ¹³C NMR, of 75% orgreater, 80% or greater, 82% or greater, 85% or greater, or 90% orgreater.

In embodiments of the present invention, the polymer has a melt index(MI) of 20 dg/min or less, 7 dg/min or less, 5 dg/min or less, or 2dg/min or less, or less than 2 dg/min. The determination of the MI ofthe polymer is according to ASTM D1238 (190° C., 2.16 kg). In thisversion of the method a portion of the sample extruded during the testwas collected and weighed. This is commonly referred to as themodification 1 of the experimental procedure. The sample analysis isconducted at 190° C. with a 1 minute preheat on the sample to provide asteady temperature for the duration of the experiment.

In one embodiment, the polymer used in the present invention isdescribed in detail as the “Second Polymer Component (SPC)” in WO00/69963, WO 00/01766, WO 99/07788, WO 02/083753, and described infurther detail as the “Propylene Olefin Copolymer” in WO 00/01745, allof which are fully incorporated by reference herein for purposes of U.S.patent practice.

The polyolefin suitable for use in the present invention can be in anyphysical form when used to blend with the NFP of the invention. In oneembodiment, reactor granules, defined as the granules of polymer thatare isolated from the polymerization reactor prior to any processingprocedures, are used to blend with the NFP of the invention. The reactorgranules have an average diameter of from 50 μm to 10 mm in oneembodiment, and from 10 μm to 5 mm in another embodiment. In anotherembodiment, the polyolefin is in the form of pellets, such as, forexample, having an average diameter of from 1 mm to 10 mm that areformed from melt extrusion of the reactor granules.

In one embodiment of the invention, the polyolefin suitable for thecomposition excludes physical blends of polypropylene with otherpolyolefins, and in particular, excludes physical blends ofpolypropylene with low molecular weight (500 to 10,000 g/mol)polyethylene or polyethylene copolymers, meaning that, low molecularweight polyethylene or polyethylene copolymers are not purposefullyadded in any amount to the polyolefin (e.g., polypropylene homopolymeror copolymer) compositions of the invention, such as is the case in, forexample, WO 01/18109 A1.

In a preferred embodiment, the NFP is an isoparaffin comprising C₆ toC₂₅ isoparaffins. In another embodiment the non-functionalizedplasticizer is a polyalphaolefin comprising C₁₀ to C₁₀₀ n-paraffins. Thepolyolefin may be a polypropylene homopolymer, copolymer, impactcopolymer, or blends thereof, and may include a plastomer. Non-limitingexamples of desirable articles of manufacture made from compositions ofthe invention include films, sheets, fibers, woven and nonwoven fabrics,tubes, pipes, automotive components, furniture, sporting equipment, foodstorage containers, transparent and semi-transparent articles, toys,tubing and pipes, and medical devices. The compositions of the inventionmay be characterized by having an improved (decreased) T_(g) relative tothe starting polyolefin, while maintaining other desirable properties.

The polyolefin and NFP can be blended by any suitable means, and aretypically blended to obtain a homogeneous, single phase mixture. Forexample, they may be blended in a tumbler, static mixer, batch mixer,extruder, or a combination thereof. The mixing step may take place aspart of a processing method used to fabricate articles, such as in theextruder on an injection molding maching or fiber line.

The enhanced properties of the plasticized polyolefin compositionsdescribed herein are useful in a wide variety of applications, includingtransparent articles such as cook and storage ware, and in otherarticles such as furniture, automotive components, toys, sportswear,medical devices, sterilizable medical devices and sterilizationcontainers, nonwoven fibers and fabrics and articles therefrom such asdrapes, gowns, filters, hygiene products, diapers, and films, orientedfilms, sheets, tubes, pipes and other items where softness, high impactstrength, and impact strength below freezing is important. Fabricationof the plasticized polyolefins of the invention to form these articlesmay be accomplished by injection molding, extrusion, thermoforming, blowmolding, rotomolding, spunbonding, meltblowing, fiber spinning, blownfilm, stretching for oriented films, and other common processingmethods.

In one embodiment of compositions of the present invention, conventionalplasticizers such as is commonly used for poly(vinyl chloride) aresubstantially absent. In particular, plasticizers such as phthalates,adipates, trimellitate esters, polyesters, and other functionalizedplasticizers as disclosed in, for example, U.S. Pat. No. 3,318,835; U.S.Pat. No. 4,409,345; WO 02/31044 A1; and PLASTICS ADDITIVES 499-504(Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially absent.By “substantially absent”, it is meant that these compounds are notadded deliberately to the compositions and if present at all, arepresent at less than 0.5 weight %.

Oils such as naphthenic and other aromatic containing oils are presentto less than 0.5 wt % of the compositions of the invention in a furtherembodiment. Also, aromatic moieties and carbon-carbon unsaturation aresubstantially absent from the non-functionalized plasticizers used inthe present invention in yet another embodiment. Aromatic moietiesinclude a compound whose molecules have the ring structurecharacteristic of benzene, naphthalene, phenanthrene, anthracene, etc.By “substantially absent”, it is meant that these aromatic compounds ormoieties are not added deliberately to the compositions, and if present,are present to less than 0.5 wt % of the composition.

In another embodiment of compositions of the present invention,conventional plasticizers, elastomers, or “compatibilizers” such as lowmolecular weight polyethylene are substantially absent. In particular,ethylene homopolymers and copolymers having a weight average molecularweight of from 500 to 10,000 are substantially absent. Such polyethylenecompatibilizers are disclosed in, for example, WO 01/18109 A1. By“substantially absent”, it is meant that these compounds are not addeddeliberately to the compositions and, if present, are present at lessthan 5 weight %, more preferably less than 4 weight %, more preferablyless than 3 weight %, more preferably less than 2 weight %, morepreferably less than 1 weight %, more preferably less than 0.5 weight %,based upon the weight of the polyolefin, the ethylene polymer orcopolymer, and the NFP.

Blending and Articles of Manufacture

The polyolefin compositions of the present invention may also containother additives. Those additives include antioxidants, nucleatingagents, acid scavengers, stabilizers, anticorrosion agents, blowingagents, other UV absorbers such as chain-breaking antioxidants, etc.,quenchers, antistatic agents, slip agents, pigments, dyes and fillersand cure agents such as peroxide. Dyes and other colorants common in theindustry may be present from 0.01 to 10 wt % in one embodiment, and from0.1 to 6 wt % in another embodiment. Suitable nucleating agents aredisclosed by, for example, H. N. Beck in Heterogeneous Nucleating Agentsfor Polypropylene Crystallization, 11 J. APPLIED POLY. SCI. 673-685(1967) and in Heterogeneous Nucleation Studies on Polypropylene, 21 J.POLY. SCI.: POLY. LETTERS 347-351 (1983). Examples of suitablenucleating agents are sodium benzoate, sodium2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, aluminum2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, dibenzylidenesorbitol, di(p-tolylidene) sorbitol, di(p-ethylbenzylidene) sorbitol,bis(3,4-dimethylbenzylidene) sorbitol, andN′,N′-dicyclohexyl-2,6-naphthalenedicarboxamide, and salts ofdisproportionated rosin esters. The foregoing list is intended to beillustrative of suitable choices of nucleating agents for inclusion inthe subject polypropylene formulations.

In particular, antioxidants and stabilizers such as organic phosphites,hindered amines, and phenolic antioxidants may be present in thepolyolefin compositions of the invention from 0.001 to 2 wt % in oneembodiment, and from 0.01 to 0.8 wt % in another embodiment, and from0.02 to 0.5 wt % in yet another embodiment. Non-limiting examples oforganic phosphites that are suitable aretris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS 168) anddi(2,4-di-tert-butylphenyl)pentaerithritol diphosphite (ULTRANOX 626).Non-limiting examples of hindered amines includepoly[2-N,N′-di(2,2,6,6-tetramethyl-4-piperidinyl)-hexanediamine-4-(1-amino-1,1,3,3-tetramethylbutane)sym-triazine](CHIMASORB 944); bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN770). Non-limiting examples of phenolic antioxidants includepentaerythrityl tetrakis(3,5-di-tert-butyl-4-hydroxyphenyl) propionate(IRGANOX 1010); and1,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl-isocyanurate (IRGANOX 3114).

Fillers may be present from 0.1 to 50 wt % in one embodiment, and from0.1 to 25 wt % of the composition in another embodiment, and from 0.2 to10 wt % in yet another embodiment. Desirable fillers include but notlimited to titanium dioxide, silicon carbide, silica (and other oxidesof silica, precipitated or not), antimony oxide, lead carbonate, zincwhite, lithopone, zircon, corundum, spinel, apatite, Barytes powder,barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate,talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr orFe and CO₃ and/or HPO₄, hydrated or not; quartz powder, hydrochloricmagnesium carbonate, glass fibers, clays, alumina, and other metaloxides and carbonates, metal hydroxides, chrome, phosphorous andbrominated flame retardants, antimony trioxide, silica, silicone, andblends thereof. These fillers may particularly include any other fillersand porous fillers and supports known in the art, and may have the NFPof the invention pre-contacted, or pre-absorbed into the filler prior toaddition to the polyolefin in one embodiment.

More particularly, in one embodiment of the present invention, the NFP,or some portion of the NFP, may be blended with a filler, desirably aporous filler. The NFP and filler may be blended by, for example, atumbler or other wet blending apparatus. The NFP and filler in thisembodiment are blended for a time suitable to form a homogenouscomposition of NFP and filler, desirably from 1 minute to 5 hours in oneembodiment. This NFP/filler blend may then be blended with thepolyolefin useful in the invention in order to effectuate plasticationof the polyolefin. In another embodiment, a porous filler may becontacted with the NFP, or some portion thereof, prior to contacting thefiller with the polyolefin. In another embodiment, the porous filler,polyolefin and NFP are contacted simultaneously (or in the same blendingapparatus). In any case, the NFP may be present from 0.1 to 60 wt % ofthe composition, and from 0.2 to 40 wt % in another embodiment, and from0.3 to 20 wt % in yet another embodiment.

Fatty acid salts may also be present in the polyolefin compositions ofthe present invention. Such salts may be present from 0.001 to 1 wt % ofthe composition in one embodiment, and from 0.01 to 0.8 wt % in anotherembodiment. Examples of fatty acid metal salts include lauric acid,stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalicacid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenicacid, oleic acid, palmitic acid, and erucic acid, suitable metalsincluding Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so forth.Preferable fatty acid salts are selected from magnesium stearate,calcium stearate, sodium stearate, zinc stearate, calcium oleate, zincoleate, and magnesium oleate.

The resultant plasticized polyolefin of the present invention may beprocessed by any suitable means such as by calendering, casting,coating, compounding, extrusion, foamed, laminated, blow molding,compression molding, injection molding, thermoforming, transfer molding,cast molding, rotational molding, casting such as for films, spun ormelt bonded such as for fibers, or other forms of processing such asdescribed in, for example, PLASTICS PROCESSING (Radian Corporation,Noyes Data Corp. 1986). More particularly, with respect to the physicalprocess of producing the blend, sufficient mixing should take place toassure that a uniform blend will be produced prior to conversion into afinished product.

More particularly, the components of the polyolefinic composition of thepresent invention may be blended by any suitable means to form theplasticized polyolefin, which is then suitable for further processinginto useful articles. In one aspect of the invention, the polyolefin andNFP are blended, or melt blended, in an apparatus such as an extruder orBrabender mixer. The polyolefin may also be blended with the NFP using atumbler, double-cone blender, ribbon blender, or other suitable blender.In yet another embodiment, the polyolefin and NFP are blended by acombination of, for example, a tumbler, followed by melt blending in anextruder. Extrusion technology for polypropylene is described in moredetail in, for example, PLASTICS LEXTRUSION TECHNOLOGY 26-37 (FriedhelmHensen, ed. Hanser Publishers 1988) and in POLYPROPYLENE HANDBOOK304-348 (Edward P. Moore, Jr. ed., Hanser Publishers 1996).

More particularly, the components of the polyolefinic composition of thepresent invention may be blended in solution by any suitable means toform the plasticized polyolefin, by using a solvent that dissolves bothcomponents to a significant extent. The blending may occur at anytemperature or pressure where the NFP and the polyolefin remain insolution. Preferred conditions include blending at high temperatures,such as 20° C. or more, preferably 40° C. or more over the melting pointof the polyolefin. For example iPP would typically be solution blendedwith the NFP at a temperature of 200° C. or more, preferably 220° C. ormore. Such solution blending would be particularly useful in processeswhere the polyolefin is made by solution process and the NFP is addeddirectly to the finishing train, rather than added to the dry polymer inanother blending step altogether. Such solution blending would also beparticularly useful in processes where the polyolefin is made in a bulkor high pressure process where the both the polymer and the NFP weresoluble in the monomer. As with the solution process the NFP is addeddirectly to the finishing train, rather than added to the dry polymer inanother blending step altogether.

The polyolefin suitable for use in the present invention can be in anyphysical form when used to blend with the NFP of the invention. In oneembodiment, reactor granules, defined as the granules of polymer thatare isolated from the polymerization reactor, are used to blend with theNFP of the invention. The reactor granules have an average diameter offrom 10 μm to 5 mm, and from 50 μm to 10 mm in another embodiment.Alternately, the polyolefin is in the form of pellets, such as, forexample, having an average diameter of from 1 mm to 6 mm that are formedfrom melt extrusion of the reactor granules.

One method of blending the NFP with the polyolefin is to contact thecomponents in a tumbler, the polyolefin being in the form of reactorgranules. This works particularly well with polypropylene homopolymer.This can then be followed, if desired, by melt blending in an extruder.Another method of blending the components is to melt blend thepolyolefin pellets with the NFP directly in an extruder or Brabender.

Thus, in the cases of injection molding of various articles, simplesolid state blends of the pellets serve equally as well as pelletizedmelt state blends of raw polymer granules, of granules with pellets, orof pellets of the two components since the forming process includes aremelting and mixing of the raw material. In the process of compressionmolding of medical devices, however, little mixing of the meltcomponents occurs, and a pelletized melt blend would be preferred oversimple solid state blends of the constituent pellets and/or granules.Those skilled in the art will be able to determine the appropriateprocedure for blending of the polymers to balance the need for intimatemixing of the component ingredients with the desire for process economy.

The polyolefinic compositions of the present invention are suitable forsuch articles as automotive components, wire and cable jacketing, pipes,agricultural films, geomembranes, toys, sporting equipment, medicaldevices, casting and blowing of packaging films, extrusion of tubing,pipes and profiles, sporting equipment, outdoor furniture (e.g., gardenfurniture) and playground equipment, boat and water craft components,and other such articles. In particular, the compositions are suitablefor automotive components such as bumpers, grills, trim parts,dashboards and instrument panels, exterior door and hood components,spoiler, wind screen, hub caps, mirror housing, body panel, protectiveside molding, and other interior and external components associated withautomobiles, trucks, boats, and other vehicles.

Other useful articles and goods may be formed economically by thepractice of our invention including: crates, containers, packaging,labware, such as roller bottles for culture growth and media bottles,office floor mats, instrumentation sample holders and sample windows;liquid storage containers such as bags, pouches, and bottles for storageand IV infusion of blood or solutions; packaging material includingthose for any medical device or drugs including unit-dose or otherblister or bubble pack as well as for wrapping or containing foodpreserved by irradiation. Other useful items include medical tubing andvalves for any medical device including infusion kits, catheters, andrespiratory therapy, as well as packaging materials for medical devicesor food which is irradiated including trays, as well as stored liquid,particularly water, milk, or juice, containers including unit servingsand bulk storage containers as well as transfer means such as tubing,pipes, and such.

These devices may be made or formed by any useful forming means forforming polyolefins. This will include, at least, molding includingcompression molding, injection molding, blow molding, and transfermolding; film blowing or casting; extrusion, and thermoforming; as wellas by lamination, pultrusion, protrusion, draw reduction, rotationalmolding, spinbonding, melt spinning, melt blowing; or combinationsthereof. Use of at least thermoforming or film applications allows forthe possibility of and derivation of benefits from uniaxial or biaxialorientation of the radiation tolerant material.

In some embodiments the plasticized polyolefins produced by thisinvention may be blended with one or more other polymers, including butnot limited to, thermoplastic polymer(s) and/or elastomer(s).By thermoplastic polymer(s)” is meant a polymer that can be melted byheat and then cooled with out appreciable change in properties.Thermoplastic polymers typically include, but are not limited to,polyolefins, polyamides, polyesters, polycarbonates, polysulfones,polyacetals, polylactones, acrylonitrile-butadiene-styrene resins,polyphenylene oxide, polyphenylene sulfide, styrene-acrylonitrileresins, styrene maleic anhydride, polyimides, aromatic polyketones, ormixtures of two or more of the above. Preferred polyolefins include, butare not limited to, polymers comprising one or more linear, branched orcyclic C2 to C40 olefins, preferably polymers comprising propylenecopolymerized with one or more C3 to C40 olefins, preferably a C3 to C20alpha olefin, more preferably C3 to C10 alpha-olefins. More preferredpolyolefins include, but are not limited to, polymers comprisingethylene including but not limited to ethylene copolymerized with a C3to C40 olefin, preferably a C3 to C20 alpha olefin, more preferablypropylene and or butene.By elastomers is meant all natural and synthetic rubbers, includingthose defined in ASTM D1566). Examples of preferred elastomers include,but are not limited to, ethylene propylene rubber, ethylene propylenediene monomer rubber, styrenic block copolymer rubbers (including SI,SIS, SB, SBS, SIBS and the like, where S=styrene, I=isobutylene, andB=butadiene), butyl rubber, halobutyl rubber, copolymers of isobutyleneand para-alkylstyrene, halogenated copolymers of isobutylene andpara-alkylstyrene, natural rubber, polyisoprene, copolymers of butadienewith acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinatedisoprene rubber, acrylonitrile chlorinated isoprene rubber,polybutadiene rubber (both cis and trans).In another embodiment, the blend comprising the NFP may further becombined with one or more of polybutene, ethylene vinyl acetate, lowdensity polyethylene (density 0.915 to less than 0.935 g/cm³) linear lowdensity polyethylene, ultra low density polyethylene (density 0.86 toless than 0.90 g/cm³), very low density polyethylene (density 0.90 toless than 0.915 g/cm³), medium density polyethylene (density 0.935 toless than 0.945 g/cm³), high density polyethylene (density 0.945 to 0.98g/cm³), ethylene vinyl acetate, ethylene methyl acrylate, copolymers ofacrylic acid, polymethylmethacrylate or any other polymers polymerizableby a high-pressure free radical process, polyvinylchloride,polybutene-1, isotactic polybutene, ABS resins, ethylene-propylenerubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic blockcopolymers, polyamides, polycarbonates, PET resins, crosslinkedpolyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymersof aromatic monomers such as polystyrene, poly-1 esters, polyacetal,polyvinylidine fluoride, polyethylene glycols and/or polyisobutylene.Preferred polymers include those available from Exxon Chemical Companyin Baytown, Tex. under the tradenames EXCEED™ and EXACT™.Tackifiers may be blended with the polymers of this invention and/orwith blends of the polymer produced by this inventions (as describedabove). Examples of useful tackifiers include, but are not limited to,aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbonresins, hydrogenated polycyclopentadiene resins, polycyclopentadieneresins, gum rosins, gum rosin esters, wood rosins, wood rosin esters,tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modifiedpolyterpenes, terpene phenolics, aromatic modified hydrogenatedpolycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenatedaliphatic aromatic resins, hydrogenated terpenes and modified terpenes,and hydrogenated rosin esters. In some embodiments the tackifier ishydrogenated. In other embodiments the tackifier is non-polar.(Non-polar meaning that the tackifier is substantially free of monomershaving polar groups. Preferably the polar groups are not present,however if they are preferably they are not present at more that 5weight %, preferably not more that 2 weight %, even more preferably nomore than 0.5 weight %.) In some embodiments the tackifier has asoftening point (Ring and Ball, as measured by ASTM E-28) of 80° C. to140° C., preferably 100° C. to 130° C. The tackifier, if present, istypically present at about 1 weight % to about 50 weight %, based uponthe weight of the blend, more preferably 10 weight % to 40 weight %,even more preferably 20 weight % to 40 weight %. Preferably however,tackifier is not present, or if present, is present at less than 10weight %, preferably less than 5 weight %, more preferably at less than1 weight %.In another embodiment the polymers of this invention, and/or blendsthereof, further comprise typical additives known in the art such asfillers, cavitating agents, antioxidants, surfactants, adjuvants,plasticizers, block, antiblock, color masterbatches, pigments, dyes,processing aids, UV stabilizers, neutralizers, lubricants, waxes, and/ornucleating agents. The additives may be present in the typicallyeffective amounts well known in the art, such as 0.001 weight % to 10weight %.Preferred fillers, cavitating agents and/or nucleating agents includetitanium dioxide, calcium carbonate, barium sulfate, silica, silicondioxide, carbon black, sand, glass beads, mineral aggregates, talc, clayand the like.Preferred antioxidants include phenolic antioxidants, such as Irganox1010, Irganox, 1076 both available from Ciba-Geigy. Preferred oilsinclude paraffinic or napthenic oils such as Primol 352, or Primol 876available from ExxonMobil Chemical France, S.A. in Paris, France. Morepreferred oils include aliphatic napthenic oils, white oils or the like.

Applications

The compositions of this invention (and blends thereof as describedabove) may be used in any known thermoplastic or elastomer application.Examples include uses in molded parts, films, tapes, sheets, tubing,hose, sheeting, wire and cable coating, adhesives, shoesoles, bumpers,gaskets, bellows, films, fibers, elastic fibers, nonwovens, spunbonds,sealants, surgical gowns and medical devices.

Adhesives

The polymers of this invention or blends thereof can be used asadhesives, either alone or combined with tackifiers. Preferredtackifiers are described above. The tackifier is typically present atabout 1 weight % to about 50 weight %, based upon the weight of theblend, more preferably 10 weight % to 40 weight %, even more preferably20 weight % to 40 weight %. Other additives, as described above, may beadded also.The adhesives of this invention can be used in any adhesive application,including but not limited to, disposables, packaging, laminates,pressure sensitive adhesives, tapes labels, wood binding, paper binding,non-wovens, road marking, reflective coatings, and the like. In apreferred embodiment the adhesives of this invention can be used fordisposable diaper and napkin chassis construction, elastic attachment indisposable goods converting, packaging, labeling, bookbinding,woodworking, and other assembly applications. Particularly preferredapplications include: baby diaper leg elastic, diaper frontal tape,diaper standing leg cuff, diaper chassis construction, diaper corestabilization, diaper liquid transfer layer, diaper outer coverlamination, diaper elastic cuff lamination, feminine napkin corestabilization, feminine napkin adhesive strip, industrial filtrationbonding, industrial filter material lamination, filter mask lamination,surgical gown lamination, surgical drape lamination, and perishableproducts packaging.

Films

The compositions described above and the blends thereof may be formedinto monolayer or multilayer films. These films may be formed by any ofthe conventional techniques known in the art including extrusion,co-extrusion, extrusion coating, lamination, blowing and casting. Thefilm may be obtained by the flat film or tubular process which may befollowed by orientation in an uniaxial direction or in two mutuallyperpendicular directions in the plane of the film. One or more of thelayers of the film may be oriented in the transverse and/or longitudinaldirections to the same or different extents. This orientation may occurbefore or after the individual layers are brought together. For examplea polyethylene layer can be extrusion coated or laminated onto anoriented polypropylene layer or the polyethylene and polypropylene canbe coextruded together into a film then oriented. Likewise, orientedpolypropylene could be laminated to oriented polyethylene or orientedpolyethylene could be coated onto polypropylene then optionally thecombination could be oriented even further. Typically the films areoriented in the Machine Direction (MD) at a ratio of up to 15,preferably between 5 and 7, and in the Transverse Direction (TD) at aratio of up to 15 preferably 7 to 9. However in another embodiment thefilm is oriented to the same extent in both the MD and TD directions.

In another embodiment the layer comprising the plasticized polyolefincomposition of this invention (and/or blends thereof) may be combinedwith one or more other layers. The other layer(s) may be any layertypically included in multilayer film structures. For example the otherlayer or layers may be:

-   1. Polyolefins-    Preferred polyolefins include homopolymers or copolymers of C2 to    C40 olefins, preferably C2 to C20 olefins, preferably a copolymer of    an alpha-olefin and another olefin or alpha-olefin (ethylene is    defined to be an alpha-olefin for purposes of this invention).    Preferably homopolyethylene, homopolypropylene, propylene    copolymerized with ethylene and or butene, ethylene copolymerized    with one or more of propylene, butene or hexene, and optional    dienes. Preferred examples include thermoplastic polymers such as    ultra low density polyethylene, very low density polyethylene,    linear low density polyethylene, low density polyethylene, medium    density polyethylene, high density polyethylene, polypropylene,    isotactic polypropylene, highly isotactic polypropylene,    syndiotactic polypropylene, random copolymer of propylene and    ethylene and/or butene and/or hexene, elastomers such as ethylene    propylene rubber, ethylene propylene diene monomer rubber, neoprene,    and blends of thermoplastic polymers and elastomers, such as for    example, thermoplastic elastomers and rubber toughened plastics.-   2. Polar polymers-    Preferred polar polymers include homopolymers and copolymers of    esters, amides, actates, anhydrides, copolymers of a C2 to C20    olefin, such as ethylene and/or propylene and/or butene with one or    more polar monomers such as acetates, anhydrides, esters, alcohol,    and or acrylics. Preferred examples include polyesters, polyamides,    ethylene vinyl acetate copolymers, and polyvinyl chloride.-   3. Cationic polymers Preferred cationic polymers include polymers or    copolymers of geminally disubstituted olefins, alpha-heteroatom    olefins and/or styrenic monomers. Preferred geminally disubstituted    olefins include isobutylene, isopentene, isoheptene, isohexane,    isooctene, isodecene, and isododecene. Preferred alpha-heteroatom    olefins include vinyl ether and vinyl carbazole, preferred styrenic    monomers include styrene, alkyl styrene, para-alkyl styrene,    alpha-methyl styrene, chloro-styrene, and bromo-para-methyl styrene.    Preferred examples of cationic polymers include butyl rubber,    isobutylene copolymerized with para methyl styrene, polystyrene, and    poly-alpha-methyl styrene.-   4. Miscellaneous-    Other preferred layers can be paper, wood, cardboard, metal, metal    foils (such as aluminum foil and tin foil), metallized surfaces,    glass (including silicon oxide (SiO.x) coatings applied by    evaporating silicon oxide onto a film surface), fabric, spunbonded    fibers, and non-wovens (particularly polypropylene spunbonded fibers    or non-wovens), and substrates coated with inks, dyes, pigments, and    the like.-    The films may vary in thickness depending on the intended    application, however films of a thickness from 1 to 250 μm are    usually suitable. Films intended for packaging are usually from 10    to 60 micron thick. The thickness of the sealing layer is typically    0.2 to 50 μm. There may be a sealing layer on both the inner and    outer surfaces of the film or the sealing layer may be present on    only the inner or the outer surface.-    Additives such as block, antiblock, antioxidants, pigments,    fillers, processing aids, UV stabilizers, neutralizers, lubricants,    surfactants and/or nucleating agents may also be present in one or    more than one layer in the films. Preferred additives include    silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes,    wax, calcium sterate, carbon black, low molecular weight resins and    glass beads.-    In another embodiment one more layers may be modified by corona    treatment, electron beam irradiation, gamma irradiation, or    microwave irradiation. In a preferred embodiment one or both of the    surface layers is modified by corona treatment.-    The films described herein may also comprise from 5 to 60 weight %,    based upon the weight of the polymer and the resin, of a hydrocarbon    resin. The resin may be combined with the polymer of the seal    layer(s) or may be combined with the polymer in the core layer(s).    The resin preferably has a softening point above 100° C., even more    preferably from 130 to 180° C. Preferred hydrocarbon resins include    those described above. The films comprising a hydrocarbon resin may    be oriented in uniaxial or biaxial directions to the same or    different degrees.    The films described above may be used as stretch and/or cling films.    Stretch/cling films are used in various bundling, packaging and    palletizing operations. To impart cling properties to, or improve    the cling properties of, a particular film, a number of well-known    tackifying additives have been utilized. Common tackifying additives    include polybutenes, terpene resins, alkali metal stearates and    hydrogenated rosins and rosin esters. The cling properties of a film    can also be modified by the well-known physical process referred to    as corona discharge. Some polymers (such as ethylene methyl acrylate    copolymers) do not need cling additives and can be used as cling    layers without tackifiers. Stretch/clings films may comprise a slip    layer comprising any suitable polyolefin or combination of    polyolefins such as polyethylene, polypropylene, copolymers of    ethylene and propylene, and polymers obtained from ethylene and/or    propylene copolymerized with minor amounts of other olefins,    particularly C.4 to C12 olefins. Particularly preferred are    polypropylene and linear low density polyethylene (LLDPE). Suitable    polypropylene is normally solid and isotactic, i.e., greater than    90% hot heptane insolubles, having wide ranging melt flow rates of    from about 0.1 to about 300 g/10 min. Additionally, the slip layer    may include one or more anticling (slip and/or antiblock) additives    which may be added during the production of the polyolefin or    subsequently blended in to improve the slip properties of this    layer. Such additives are well-known in the art and include, for    example, silicas, silicates, diatomaceous earths, talcs and various    lubricants. These additives are preferably utilized in amounts    ranging from about 100 ppm to about 20,000 ppm, more preferably    between about 500 ppm to about 10,000 ppm, by weight based upon the    weight of the slip layer.

The slip layer may, if desired, also include one or more other additivesas described above

Molded Products

The plasticized polyolefin composition described above may also be usedto prepare the molded products of this invention in any molding process,including but not limited to, injection molding, gas-assisted injectionmolding, extrusion blow molding, injection blow molding, injectionstretch blow molding, compression molding, rotational molding, foammolding, thermoforming, sheet extrusion, and profile extrusion. Themolding processes are well known to those of ordinary skill in the art.

The compositions described herein may be shaped into desirable end usearticles by any suitable means known in the art. Thermoforming, vacuumforming, blow molding, rotational molding, slush molding, transfermolding, wet lay-up or contact molding, cast molding, cold formingmatched-die molding, injection molding, spray techniques, profileco-extrusion, or combinations thereof are typically used methods.

Thermoforming is a process of forming at least one pliable plastic sheetinto a desired shape. An embodiment of a thermoforming sequence isdescribed, however this should not be construed as limiting thethermoforming methods useful with the compositions of this invention.First, an extrudate film of the composition of this invention (and anyother layers or materials) is placed on a shuttle rack to hold it duringheating. The shuttle rack indexes into the oven which pre-heats the filmbefore forming. Once the film is heated, the shuttle rack indexes backto the forming tool. The film is then vacuumed onto the forming tool tohold it in place and the forming tool is closed. The forming tool can beeither “male” or “female” type tools. The tool stays closed to cool thefilm and the tool is then opened. The shaped laminate is then removedfrom the tool.

Thermoforming is accomplished by vacuum, positive air pressure,plug-assisted vacuum forming, or combinations and variations of these,once the sheet of material reaches thermoforming temperatures, typicallyof from 140° C. to 185° C. or higher. A pre-stretched bubble step isused, especially on large parts, to improve material distribution. Inone embodiment, an articulating rack lifts the heated laminate towards amale forming tool, assisted by the application of a vacuum from orificesin the male forming tool. Once the laminate is firmly formed about themale forming tool, the thermoformed shaped laminate is then cooled,typically by blowers. Plug-assisted forming is generally used for small,deep drawn parts. Plug material, design, and timing can be critical tooptimization of the process. Plugs made from insulating foam avoidpremature quenching of the plastic. The plug shape is usually similar tothe mold cavity, but smaller and without part detail. A round plugbottom will usually promote even material distribution and uniformside-wall thickness. For a semicrystalline polymer such aspolypropylene, fast plug speeds generally provide the best materialdistribution in the part.

The shaped laminate is then cooled in the mold. Sufficient cooling tomaintain a mold temperature of 30° C. to 65° C. is desirable. The partis below 90° C. to 100° C. before ejection in one embodiment. For thegood behavior in thermoforming, the lowest melt flow rate polymers aredesirable. The shaped laminate is then trimmed of excess laminatematerial.

Blow molding is another suitable forming means, which includes injectionblow molding, multi-layer blow molding, extrusion blow molding, andstretch blow molding, and is especially suitable for substantiallyclosed or hollow objects, such as, for example, gas tanks and otherfluid containers. Blow molding is described in more detail in, forexample, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92(Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).

In yet another embodiment of the formation and shaping process, profileco-extrusion can be used. The profile co-extrusion process parametersare as above for the blow molding process, except the die temperatures(dual zone top and bottom) range from 150° C.-235° C., the feed blocksare from 90° C.-250° C., and the water cooling tank temperatures arefrom 10° C.-40° C.

One embodiment of an injection molding process is described as follows.The shaped laminate is placed into the injection molding tool. The moldis closed and the substrate material is injected into the mold. Thesubstrate material has a melt temperature between 200° C. and 300° C. inone embodiment, and from 215° C. and 250° C. and is injected into themold at an injection speed of between 2 and 10 seconds. After injection,the material is packed or held at a predetermined time and pressure tomake the part dimensionally and aesthetically correct. Typical timeperiods are from 5 to 25 seconds and pressures from 1,380 kPa to 10,400kPa. The mold is cooled between 10° C. and 70° C. to cool the substrate.The temperature will depend on the desired gloss and appearance desired.Typical cooling time is from 10 to 30 seconds, depending on part on thethickness. Finally, the mold is opened and the shaped composite articleejected.

Likewise, molded articles may be fabricated by injecting molten polymerinto a mold that shapes and solidifies the molten polymer into desirablegeometry and thickness of molded articles. Sheet may be made either byextruding a substantially flat profile from a die, onto a chill roll, oralternatively by calendaring. Sheet will generally be considered to havea thickness of from 10 mils to 100 mils (254 μm to 2540 μm), althoughsheet may be substantially thicker. Tubing or pipe may be obtained byprofile extrusion for uses in medical, potable water, land drainageapplications or the like. The profile extrusion process involves theextrusion of molten polymer through a die. The extruded tubing or pipeis then solidified by chill water or cooling air into a continuousextruded articles. The tubing will generally be in the range of from0.31 cm to 2.54 cm in outside diameter, and have a wall thickness of inthe range of from 254 μm to 0.5 cm. The pipe will generally be in therange of from 2.54 cm to 254 cm in outside diameter, and have a wallthickness of in the range of from 0.5 cm to 15 cm. Sheet made from theproducts of an embodiment of a version of the present invention may beused to form containers. Such containers may be formed by thermoforming,solid phase pressure forming, stamping and other shaping techniques.Sheets may also be formed to cover floors or walls or other surfaces.

In an embodiment of the thermoforming process, the oven temperature isbetween 160° C. and 195° C., the time in the oven between 10 and 20seconds, and the die temperature, typically a male die, between 10° C.and 71° C. The final thickness of the cooled (room temperature), shapedlaminate is from 10 μm to 6000 μm in one embodiment, from 200 μm to 6000μm in another embodiment, and from 250 μm to 3000 μm in yet anotherembodiment, and from 500 μm to 1550 μm in yet another embodiment, adesirable range being any combination of any upper thickness limit withany lower thickness limit.

In an embodiment of the injection molding process, wherein a substratematerial in injection molded into a tool including the shaped laminate,the melt temperature of the substrate material is between 230° C. and255° C. in one embodiment, and between 235° C. and 250° C. in anotherembodiment, the fill time from 2 to 10 seconds in one embodiment, from 2to 8 seconds in another embodiment, and a tool temperature of from 25°C. to 65° C. in one embodiment, and from 27° C. and 60° C. in anotherembodiment. In a desirable embodiment, the substrate material is at atemperature that is hot enough to melt any tie-layer material or backinglayer to achieve adhesion between the layers.

In yet another embodiment of the invention, the compositions of thisinvention may be secured to a substrate material using a blow moldingoperation. Blow molding is particularly useful in such applications asfor making closed articles such as fuel tanks and other fluidcontainers, playground equipment, outdoor furniture and small enclosedstructures. In one embodiment of this process, Compositions of thisinvention are extruded through a multi-layer head, followed by placementof the uncooled laminate into a parison in the mold. The mold, witheither male or female patterns inside, is then closed and air is blowninto the mold to form the part.

It will be understood by those skilled in the art that the stepsoutlined above may be varied, depending upon the desired result. Forexample, the an extruded sheet of the compositions of this invention maybe directly thermoformed or blow molded without cooling, thus skipping acooling step. Other parameters may be varied as well in order to achievea finished composite article having desirable features.

Non-Wovens and Fibers

The plasticized polyolefin composition described above may also be usedto prepare the nonwoven fabrics and fibers of this invention in anynonwoven fabric and fiber making process, including but not limited to,melt blowing, spunbonding, film aperturing, and staple fiber carding. Acontinuous filament process may also be used. Preferably a spunbondingprocess is used. The spunbonding process is well known in the art.Generally it involves the extrusion of fibers through a spinneret. Thesefibers are then drawn using high velocity air and laid on an endlessbelt. A calender roll is generally then used to heat the web and bondthe fibers to one another although other techniques may be used such assonic bonding and adhesive bonding. The fabric may be prepared withmixed metallocene polypropylene alone, physically blended with othermixed metallocene polypropylene or physically blended with singlemetallocene polypropylene. Likewise the fabrics of this invention may beprepared with mixed metallocene polypropylene physically blended withconventional Ziegler-Natta produced polymer. If blended, the fabric ofthis invention is preferably comprised of at least 50% mixed metallocenepolypropylene. With these nonwoven fabrics, manufacturers can maintainthe desirable properties of fabrics prepared with metallocene producedpolypropylene while increasing fabric strength and potentially increasedline speed compared to fabrics made using conventional polymers.

Test Methods Dynamic Mechanical Thermal Analysis

The glass transition temperature (T_(g)) and storage modulus (E′) weremeasured using dynamic mechanical thermal analysis (DMTA). This testprovides information about the small-strain mechanical response(relaxation behavior) of a sample as a function of temperature over atemperature range that includes the glass transition region and thevisco-elastic region prior to melting.

Typically, samples were tested using a three point bending configuration(TA Instruments DMA 2980). A solid rectangular compression molded barwas placed on two fixed supports; a movable clamp applied a periodicdeformation to the sample midpoint at a frequency of 1 Hz and anamplitude of 20 μm. The sample was initially cooled to −130° C. thenheated to 60° C. at a heating rate of 3° C./min. In some cases,compression molded bars were tested using other deformationconfigurations, namely dual cantilever bending and tensile elongation(Rheometrics RSAII). The periodic deformation under these configurationswas applied at a frequency of 1 Hz and strain amplitude of 0.05%. Thesample was cooled to −130° C. and then heated to 60° C. at a rate of 2°C./min. The slightly difference in heating rate does not influence theglass transition temperature measurements significantly.

The output of these DMTA experiments is the storage modulus (E′) andloss modulus (E″). The storage modulus measures the elastic response orthe ability of the material to store energy, and the loss modulusmeasures the viscous response or the ability of the material todissipate energy. Tan δ is the ratio of E″/E′ and gives a measure of thedamping ability of the material. The beginning of the broad glasstransition (β-relaxation) is identified as the extrapolated tangent tothe Tan δ peak. In addition, the peak temperature and area under thepeak are also measured to more fully characterize the transition fromglassy to visco-elastic region.

Differential Scanning Calorimetry

Crystallization temperature (T_(c)) and melting temperature (T_(m)) weremeasured using Differential Scanning Calorimetry (DSC). This analysiswas conducted using either a TA Instruments MDSC 2920 or a Perkin ElmerDSC7. Typically, 6 to 10 mg of molded polymer or plasticized polymer wassealed in an aluminum pan and loaded into the instrument at roomtemperature. Melting data (first heat) were acquired by heating thesample to at least 30° C. above its melting temperature at a heatingrate of 10° C./min. This provides information on the melting behaviorunder as-molded conditions, which can be influenced by thermal historyas well as any molded-in orientation or stresses. The sample was thenheld for 10 minutes at this temperature to destroy its thermal history.Crystallization data was acquired by cooling the sample from the melt toat least 50° C. below the crystallization temperature at a cooling rateof 10° C./min. The sample was then held at 25° C. for 10 minutes, andfinally heated at 10° C./min to acquire additional melting data (secondheat). This provides information about the melting behavior after acontrolled thermal history and free from potential molded-in orientationand stress effects. The endothermic melting transition (first and secondheat) and exothermic crystallization transition were analyzed for onsetof transition and peak temperature. The melting temperatures reported inthe tables are the peak melting temperatures from the second heat unlessotherwise indicated. For polymers displaying multiple peaks, the highermelting peak temperature is reported.

Areas under the curve was used to determine the heat of fusion (ΔH_(f))which can be used to calculate the degree of crystallinity. A value of207 J/g was used as the equilibrium heat of fusion for 100% crystallinepolypropylene (obtained from B. Wunderlich, “Thermal Analysis”, AcademicPress, Page 418, 1990). The percent crystallinity is calculated usingthe formula, [area under the curve (J/g)/207 (J/g)]*100.

Size-Exclusion Chromatography of Polymers

Molecular weight distribution was characterized using Size-ExclusionChromatography (SEC). Molecular weight (weight-average molecular weight,Mw, and number-average molecular weight, Mn) were determined using aHigh Temperature Size Exclusion Chromatograph (either from WatersCorporation or Polymer Laboratories), equipped with a differentialrefractive index detector (DRI), an online light scattering detector,and a viscometer. Experimental details not described below, includinghow the detectors were calibrated, are described in: T. Sun, P. Brant,R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19,6812-6820, (2001).

Three Polymer Laboratories PLgel 10 mm Mixed-B columns were used. Thenominal flow rate was 0.5 cm³/min, and the nominal injection volume was300 μL. The various transfer lines, columns and differentialrefractometer (the DRI detector) were contained in an oven maintained at135° C.

Solvent for the SEC experiment was prepared by dissolving 6 grams ofbutylated hydroxy toluene as an antioxidant in 4 liters of Aldrichreagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture was thenfiltered through a 0.7 μm glass pre-filter and subsequently through a0.1 μm Teflon filter. The TCB was then degassed with an online degasserbefore entering the SEC.

Polymer solutions were prepared by placing dry polymer in a glasscontainer, adding the desired amount of TCB, then heating the mixture at160° C. with continuous agitation for about 2 hours. All quantities weremeasured gravimetrically. The TCB densities used to express the polymerconcentration in mass/volume units are 1.463 g/ml at room temperatureand 1.324 g/ml at 135° C. The injection concentration ranged from 1.0 to2.0 mg/ml, with lower concentrations being used for higher molecularweight samples.

Prior to running each sample the DRI detector and the injector werepurged. Flow rate in the apparatus was then increased to 0.5 ml/minute,and the DRI was allowed to stabilize for 8-9 hours before injecting thefirst sample. The LS laser was turned on 1 to 1.5 hours before runningsamples.

The concentration, c, at each point in the chromatogram is calculatedfrom the baseline-subtracted DRI signal, I_(DRI), using the followingequation:

c=K _(DRI) /I _(DRI)/(dn/dc)

where K_(DRI) is a constant determined by calibrating the DRI, and(dn/dc) is the same as described below for the LS analysis. Units onparameters throughout this description of the SEC method are such thatconcentration is expressed in g/cm³, molecular weight is expressed ing/mole, and intrinsic viscosity is expressed in dL/g.

The light scattering detector used was a Wyatt Technology HighTemperature mini-DAWN. The polymer molecular weight, M, at each point inthe chromatogram is determined by analyzing the LS output using the Zimmmodel for static light scattering (M. B. Huglin, LIGHT SCATTERING FROMPOLYMER SOLUTIONS, Academic Press, 1971):

$\frac{K_{O}c}{\Delta \; {R(\theta)}} = {\frac{1}{{MP}(\theta)} + {2A_{c}c}}$

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity atscattering angle θ, c is the polymer concentration determined from theDRI analysis, A₂ is the second virial coefficient, P(θ) is the formfactor for a monodisperse random coil (described in the abovereference), and K_(o) is the optical constant for the system:

$K_{O} = \frac{4\pi^{2}{n^{2}\left( {{n}/{c}} \right)}^{2}}{\lambda^{4}N_{A}}$

in which N_(A) is Avogadro's number, and (dn/dc) is the refractive indexincrement for the system. The refractive index, n=1.500 for TCB at 135°C. and X=690 nm. In addition, A₂=0.0006 for propylene polymers and0.0015 for butene polymers, and (dn/dc)=0.104 for propylene polymers and0.098 for butene polymers.

A high temperature Viscotek Corporation viscometer was used, which hasfour capillaries arranged in a Wheatstone bridge configuration with twopressure transducers. One transducer measures the total pressure dropacross the detector, and the other, positioned between the two sides ofthe bridge, measures a differential pressure. The specific viscosity,η_(s), for the solution flowing through the viscometer is calculatedfrom their outputs. The intrinsic viscosity, [η], at each point in thechromatogram is calculated from the following equation:

η_(s) =c[η]+0.3(c[η])²

where c was determined from the DRI output.

The branching index (g′) is calculated using the output of theSEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,[η]_(avg), of the sample is calculated by:

$\lbrack\eta\rbrack_{avg} = \frac{\sum{c_{i}\lbrack\eta\rbrack}_{i}}{\sum c_{i}}$

where the summations are over the chromotographic slices, i, between theintegration limits. The branching index g′ is defined as:

$g^{\prime} = \frac{\lbrack\eta\rbrack_{avg}}{{kM}_{v}^{\alpha}}$

where k=0.0002288 and α=0.705 for propylene polymers, and k=0.00018 andα=0.7 for butene polymers. M_(v) is the viscosity-average molecularweight based on molecular weights determined by LS analysis.

¹³C-NMR Spectroscopy

Polymer microstructure was determined by ¹³C-NMR spectroscopy, includingthe concentration of isotactic and syndiotactic diads ([m] and [r]),triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). Samples weredissolved in d₂-1,1,2,2-tetrachloroethane. Spectra were recorded at 125°C. using a NMR spectrometer of 75 or 100 MHz. Polymer resonance peaksare referenced to mmmm=21.8 ppm. Calculations involved in thecharacterization of polymers by NMR follow the work of F. A. Bovey in“Polymer Conformation and Configuration” Academic Press, New York 1969and J. Randall in “Polymer Sequence Determination, ¹³C-NMR Method”,Academic Press, New York, 1977. The percent of methylene sequences oftwo in length, % (CH₂)₂, were calculated as follows: the integral of themethyl carbons between 14-18 ppm (which are equivalent in concentrationto the number of methylenes in sequences of two in length) divided bythe sum of the integral of the methylene sequences of one in lengthbetween 45-49 ppm and the integral of the methyl carbons between 14-18ppm, times 100. This is a minimum calculation for the amount ofmethylene groups contained in a sequence of two or more since methylenesequences of greater than two have been excluded. Assignments were basedon H. N. Cheng and J. A. Ewen, Makromol. Chem. 1989, 190, 1931.

Viscosity of Polymers and Blends

The shear viscosity as a function of shear rate was determined using adual-barrel capillary rheometer. The capillary rheometer (Rosand ModelRAH7/2 by Bohun Instruments) was equipped with a 30:1 length to diameterratio capillary. A total mass of 25-30 g of pellets were packed into thecapillary barrels and preheated at 230° C. for 10 minutes to remove anyentrained air before the test. Each test was performed at 230° C. overthe shear rate range of from 30 to 3000 s⁻¹. Corrections to the data forentrance pressure losses (i.e., the Bagley correction) were performedon-line via simultaneous pressure loss measurements for the flow of thematerial through an orifice that was installed into the second barrel ofthe rheometer.

The dynamic shear viscosity as a function of frequency was determined bysmall-amplitude oscillatory shear rheology. A Rheometrics ScientificDSR-500 dynamic stress-controlled rheometer with a cone and plate samplefixture was used. Testing was performed at 190° C. Samples weresubjected to an oscillatory shear stress at a nominal amplitude of 100Pa by oscillating the upper cone at a fixed frequency, and the resultantstrain was measured. The auto-stress adjustment capability was utilizedto keep the strain within limits of 1-30% (stress adjustment setting=32%of current stress, maximum stress=100 Pa). These conditions ensure thateach material was characterized within its linear viscoelastic region.The dynamic shear viscosity was calculated from the measured strain andapplied stress as a function of frequency. Frequency sweeps wereconducted starting at 500 rad/s and decreasing to 0.02 rad/s, using alogarithmic sweep mode with 6 points per decade.

The dynamic viscosity (η*) versus frequency (ω) curves were fitted usingthe Cross model (as described in C. W. Macoskco, “Rheology: Principles,Measurements, and Applications”, Wiley-VCH, 1994):

$\eta^{*} = \frac{\eta_{0}}{1 + \left( {\lambda \; \omega} \right)^{1 - n}}$

The three parameters in this model are: η₀, the zero-shear viscosity; λ,the average relaxation time; and n, the power law exponent. Thezero-shear viscosity is the value at a plateau in the Newtonian regionof the flow curve at a low frequency, where the dynamic viscosity isindependent of frequency. The average relaxation time corresponds to theinverse of the frequency at which shear-thinning starts. The power lawexponent n is the slope of the shear thinning region at high shear ratesin a log-log plot of dynamic viscosity versus frequency. Theseparameters provide a means to compare the effect of plasticization on amaterial's flow behavior, sensitivity to shear, and molecular structure.

Melt Flow Rate of Polymers and Blends

Melt Flow Rate (MFR) is measured according to ASTM D1238 at 230° C.under a load of 2.16 kg. Melt Index (MI) is measured according to ASTM D1238 at 190° C. under a load of 2.16 kg. The units are g/10 min, ordg/min.

Polymer Density

Density is measured by density-gradient column, such as described inASTM D1505, on a compression-molded specimen that has been slowly cooledto room temperature.

Mechanical Properties

Test specimens for mechanical property testing were injection-molded,unless otherwise specified. The testing temperature was standardlaboratory temperature (23±2° C.) as specified in ASTM D618, unlessotherwise specified. Instron load frames were used for tensile andflexure testing.

Tensile properties were determined according to ASTM D638, includingYoung's modulus (also called modulus of elasticity), yield stress (alsocalled tensile strength at yield), yield strain (also called elongationat yield), break stress (also called tensile strength at break), andbreak strain (also called elongation at break). The energy to yield isdefined as the area under the stress-strain curve from zero strain tothe yield strain. The energy to break is defined as the area under thestress-strain from zero strain to the break strain. Injection-moldedtensile bars were of either ASTM D638 Type I or Type IV geometry, testedat a speed of 2 inch/min. Compression-molded tensile bars were of ASTMD412 Type C geometry, tested at a speed of 20 inch/min. Forcompression-molded specimens only: the yield stress and yield strainwere determined as the 10% offset values as defined in ASTM D638. Breakproperties were reported only if a majority of test specimens brokebefore a strain of about 2000%, which is the maximum strain possible onthe load frame used for testing.

Flexure properties were determined according to ASTM D790A, includingthe 1% secant modulus and 2% secant modulus. Test specimen geometry wasas specified under “Molding Materials (Thermoplastics and Thermosets)”,and the support span was 2 inches.

Heat deflection temperature was determined according to ASTM D648, at 66psi, on injection-molded specimens.

Rockwell hardness was determined according to ASTM D785, using theR-scale.

Impact Properties

Gardner impact strength was determined according to ASTM D5420, on 0.125inch thick injection-molded disks, at the specified temperature.

Notched izod impact resistance was determined according to ASTM D256, atthe specified temperature. A TMI Izod Impact Tester was used. Specimenswere either cut individually from the center portion of injection-moldedASTM D638 Type I tensile bars, or pairs of specimens were made bycutting injection-molded ASTM D790 “Molding Materials (Thermoplasticsand Thermosets)” bars in half. The notch was oriented such that theimpact occurred on the notched side of the specimen (following ProcedureA of ASTM D256) in most cases; where specified, the notch orientationwas reversed (following Procedure E of ASTM D256). All specimens wereassigned a thickness of 0.122 inch for calculation of the impactresistance. All breaks were complete, unless specified otherwise.

Optical Properties

Haze was determined by ASTM D1003, on a 0.04 inch think injection-moldedplaque. Gloss was determined by ASTM D2457, at an angle of 45°.

Fabric and Film Properties

Flexure and tensile properties (including 1% Secant Flexure Modulus,Peak Load, Tensile Strength at Break, and Elongation at Break) aredetermined by ASTM D 882. Elmendorf tear is determined by ASTM D 1922.Puncture and puncture energy are determined by ASTM D 3420. Total energydart impact is determined by ASTM D 4272 Softness or “hand” of spunbondnonwoven fabric as it is known in the art was measured using theThwing-Albert Handle-O-Meter (Model 211-10-B/America.) The quality of“hand” is considered to be the combination of resistance due to thesurface friction and flexibility of a fabric material. TheHandle-O-Meter measures the above two factors using and LVDT (LinearVariable Differential Transformer) to detect the resistance that a bladeencounters when forcing a specimen of material into a slot of paralleledges. A 3½ digit digital voltmeter (DVM) indicates the resistancedirectly in grams. The “total hand” of any given sheet of material isthe average of four readings taken on both sides and both directions ofa test sample and is recorded in grams per standard width of samplematerial. A decrease in “total hand” indicates the improvement of fabricsoftness.

Fluid Properties

Pour Point is measured by ASTM D 97. Kinematic Viscosity (KV) ismeasured by ASTM D 445. Specific gravity is typically determined by ASTMD 4052, at the temperature specified. Viscosity index (VI) is determinedby ASTM D 2270. Boiling point and distillation range are typicallydetermined by ASTM D 86 or ASTM D 1160. Saturates and aromatics contentcan be determined by various methods, such as ASTM D 3238.

The number-average molecular weight (Mn) can be determined by GasChromatography (GC), as described in “Modern Practice of GasChromatography”, R. L. Grob and E. F. Barry, Wiley-Interscience, 3rdEdition (July 1995); or determined by Gel Permeation Chromatography(GPC), as described in “Modern Size Exclusion Liquid Chromatographs”, W.W. Yan, J. J. Kirkland, and D. D. Bly, J. Wiley & Sons (1979); orestimated by ASTM D 2502; or estimated by freezing point depression, asdescribed in “Lange's Handbook of Chemistry”, 15th Edition, McGrawHill.The average carbon number (Cn) is calculated from Mn by Cn=(Mn−2)/14.

Processing Methods Blending

The components of the present invention can be blended by any suitablemeans. For example, they may be blended in a static mixer, batch mixer,extruder, or a combination thereof, that is sufficient to achieve anadequate dispersion of plasticizer in the polymer. The mixing step mayinvolve first dry blending using, for example, a tumble blender.Dispersion may take place as part of a processing method used tofabricate articles, such as in the extruder on an injection moldingmaching or fiber line. The plasticizer may be injected into the extruderbarrel or introduced at the feed throat of the extruder to save the stepof preblending. This is a preferred method when a larger percentage ofplasticizer is to be used.

Two general methods were used to generate examples of plasticizedblends. The first method, which is referred to as the Extruder Method,involved first “dry blending” reactor granules of the polymer withappropriate amounts of plasticizer and an additive package (includingsuch components as antioxidants and nucleating agents) in a tumbleblender to achieve a homogeneous mixing of components at the desiredplasticizer and additive concentrations. This was followed bycompounding and pelletizing the blend using an extruder (either a 30 or57 mm twin screw extruder) at an appropriate extrusion temperature abovethe melting point of the polymer, but always in the range of 200-230° C.In some cases, a sample of desired plasticizer concentration wasproduced by adding neat polymer pellets to plasticized polymer pelletsthat had been blended previously at a higher plasticizer concentration.

The second method, which is referred to as the Brabender Method,involved mixing polymer pellets with the plasticizer in a heated C. W.Brabender Instruments Plasticorder to achieve a homogeneous melt at thedesired plasticizer concentration. The Brabender was equipped with aPrep-Mixer head (approximately 200 cm³ volume) and roller blades. Theoperating temperature was above the melting point of the polymer, butalways in the range of 180-190° C. Polymer was first melted in theBrabender for 1 minute at 60 RPM. Plasticizer was then added slowly toprevent pooling in the melted polymer. The blend was then mixed for 5minutes at 60 RPM under a nitrogen purge. The Brabender was opened andthe melt removed from the mixing head and blades as quickly as possible,and allowed to solidify. For those blends later subjected to injectionmolding, the pieces of material from the Brabender were cut into smallerpieces using a guillotine, then ground into even smaller pieces using aWiley Mill.

Injection Molding

For materials blended using the Extruder Method, standard ASTM tensileand HDT bars, and Gardner impact discs, were molded using 120 toninjection molding equipment according to ASTM D4101. For materialsblended using the Brabender Method, tensile and flexure bars were moldedusing 20 ton injection molding equipment according to ASTM D4101, exceptfor the following provisions: the mold temperature was 40° C.; theinject time was 30 sec; the tensile and flex bars were of ASTM D638 TypeIV and ASTM D790 geometries, respectively; and the melt temperature was,in some cases, 10° C. off from the ASTM D4101-specified value, butalways in the range of 190-200° C. (except for the polybutene blends,which were molded with a melt temperature in the range of 220-230° C.).

Compression Molding

Material to be molded was placed between two sheets of PTFE-coatedaluminum foil onto a 0.125 inch thick chase, and pressed in a Carverpress at 160° C. The material was allowed to melt for 5 minutes withoutpressure applied, then compressed for 5 minutes at 10 tons pressure. Itwas then removed and immediately placed between water-cooled coldplatens and pressed for another 5 minutes at 10 tons pressure. Thefoil-sample-foil assembly was allowed to anneal for at least 40 hours atroom temperature, then quenched in dry ice prior to removing the samplefrom the foil to prevent deformation of the material when peeling offthe foil. Tensile and flexure specimens were died out of the sample onceit warmed to room temperature.

Spunbond Fabric Process

A typical spunbond process consists of a continuous filament extrusion,followed by drawing, web formation by the use of some type of ejector,and bonding the web. The polymer pellets are first fed into an extruder.In the extruder, the pellets simultaneously are melted and forcedthrough the system by a heating melting screw. At the end of the screw,a spinning pump meters the molten polymer through a filter to aspinneret where the molten polymer is extruded under pressure throughcapillaries, at a rate of 0.4 grams per hole per minute. The spinneretcontains a few hundred capillaries, measuring 0.4 mm in diameter. Thepolymer is melted at about 30-50° C. above its melting point to achievesufficiently low melt viscosity for extrusion. The fibers exiting thespinneret are quenched and drawn into fine fibers measuring about 16microns in diameter. The solidified fiber is laid randomly on a movingbelt to form a random netlike structure known in the art as web. The 25basis weight (grams per square meter) of web is obtained by controllingthe belt moving speed. After web formation, the web is bonded to achieveits final strength using a heated textile calender known in the art asthermobond calender. The calender consists of two heated steel rolls;one roll is plain and the other bears a pattern of raised points. Theweb is conveyed to the calender wherein a fabric is formed by pressingthe web between the rolls at a bonding temperature of about 138° C.

Cast Film Process

Cast films were prepared using the following operations. Cast monolayerfilms were fabricated on a Killion cast film line. This line has three24:1 L/D 2.54 cm diameter extruder, which feed polymer into a feedblock.The feedblock diverts molten polymer from the extruder to a 20.32 cmwide Cloeren die. Molten polymer exits the die at a temperature of 230°C. and is cast on a chill roll (20.3 cm diameter, 25.4 cm roll face) at21° C. The casting unit is equipped with adjustable winding speeds toobtain film of the targeted thickness.

Methods for Determining NFP Content in Blend Method 1: Extraction

One method to determine the amount of NFP in a blend is Soxhletextraction, wherein at least a majority of the NFP is extracted withrefluxing n-heptane. Analysis of the base polymer is also requiredbecause it may contain low molecular weight and/or amorphous materialthat is soluble in refluxing n-heptane. The level of plasticizer in theblend is determined by correcting its extractables level, in weightpercent, by the extractables level for the base polymer, as describedbelow.

The Soxhlet extraction apparatus consists of a 400 ml Soxhlet extractor,with a widened overflow tube (to prevent siphoning and to provideconstant flow extraction); a metal screen cage fitted inside the mainSoxhlet chamber; a Soxhlet extraction thimble (Whatman, singlethickness, cellulose) placed inside the screen cage; a condenser withcooling water and drain; and a one-neck 1000 ml round bottom flask withappropriately sized stir bar and heating mantle.

The procedure is as follows. Dry the soxhlet thimbles in a 95° C. ovenfor ˜60 minutes. Weigh the dry thimble directly after removal from oven;record this weight as A: Thimble Weight Before, in g. Weigh out 15-20grams of sample (either in pellet or ground pellet form) into thethimble; record as B: Polymer Weight, in g. Place the thimble containingthe polymer in the Soxhlet apparatus. Pour about 300 ml of HPLC-graden-heptane into the round bottom flask with stir bar and secure the flaskon the heating mantle. Connect the round bottom flask, the soxhlet, andthe condenser in series. Pour more n-heptane down through the center ofthe condenser into the Soxhlet main chamber until the solvent level isjust below the top of the overflow tube. Turn on the cooling water tothe condenser. Turn on the heating mantle and adjust the setting togenerate a rolling boil in the round bottom flask and maintain a goodreflux. Allow to reflux for 16 hours. Turn the heat off but leave thecooling system on. Allow the system to cool down to room temperature.Disassemble the apparatus. Remove the thimble and rinse with a smallamount of fresh n-heptane. Allow to air dry in the laboratory hood,followed by oven drying at 95° C. for 90 minutes. Weigh the thimblecontaining the polymer directly after removal from oven; record as C:Polymer/Thimble Weight After, in g.

The quantity of extract is determined by calculating the weight lossfrom the sample, W=(A+B−C), in g. The extractables level, E, in weightpercent, is then calculated by E=100(W/B). The plasticizer content inthe blend, P, in weight percent, is calculated by P=E(blend)−E(basepolymer).

Method 2: Crystallization Analysis Fractionation (CRYSTAF)

Another method to determine the amount of NFP in a blend isfractionation using the Crystallization Analysis Fractionation (CRYSTAF)technique. This technique involves dissolving a sample in a solvent athigh temperature, then cooling the solution slowly to causefractionation of the sample based on solubility. For semi-crystallinesamples, including blends, solubility depends primarily oncrystallizability: portions of the sample that are more crystalline willprecipitate out of solution at a higher temperature than portions of thesample that are less crystalline. The relative amount of sample insolution as a function of temperature is measured using an infrared (IR)detector to obtain the cumulative solubility distribution. The solublefraction (SF) is defined as the IR signal at the lowest temperaturedivided by the IR signal when all the sample is dissolved at hightemperature, and corresponds to the weight fraction of sample that hasnot crystallized.

In the case of plasticized polyolefins, the plasticizer is mostlyamorphous and therefore contributes to the SF. Thus, the SF will belarger for blends with higher plasticizer content. This relationship isexploited to determine the plasticizer content of a blend of knowncomposition (polymer and plasticizer types) but unknown concentration. Acalibration curve that describes the SF as a function of plasticizercontent is developed by making a series of physical blends of knownconcentration using the same polymer and plasticizer materials, and thenanalyzing these blends under the same run conditions as used for blendsof unknown concentration. This series of calibrants must includeplasticizer concentrations above and below the concentration of theunknown sample(s), but not greater than 50 weight percent plasticizer,in order to reliably apply the calibration curve to the unknownsample(s). Typically, a linear fit of the calibration points is found toprovide a good description of the SF as a function of plasticizercontent (R²>0.9); other functional forms with 2 or fewer fittingparameters may be used if they improve the goodness-of-fit (increaseR²).

A commercial CRYSTAF 200 instrument (Polymer Char S.A., Valencia, Spain)with five stirred stainless steel vessels of 60 mL volume was used toperform this test. Approximately 30 mg of sample were dissolved for 60min at 160° C. in 30 mL of 1,2-dichlorobenzene that was stabilized with2 g/4 L of butylated hydroxytoluene. The solution was then stabilizedfor 45 min at 100° C. The crystallization was carried out from 100 to30° C. at a crystallization rate of 0.2° C./min. A dual wavelengthinfrared detector with a heated flow through cell maintained at 150° C.was used to measure the polymer concentration in solution at regularintervals during the crystallization cycle; the measuring wavelength was3.5 μm and the reference wavelength was 3.6 μm.

Examples

The present invention, while not meant to be limiting by, may be betterunderstood by reference to the following examples and tables.

Examples Made Using the Extruder Method

Samples 1-9 were blended using the Extruder Method; the additive packagecontained 600 ppm of Irganox 1076 and 260 ppm of calcium stearate; a 57mm twin-screw extruder was used at an extrusion temperature of 230° C.Samples 10-14 were blended using the Extruder Method; the additivepackage contained 825 ppm calcium stearate, 800 ppm of Ultranox 626, 500ppm of Tinuvin 622, and 2500 ppm of Millad 3940; a 30 mm twin-screwextruder was used at an extrusion temperature of 216° C. Samples 15-19were blended using the Extruder Method; the additive package contained800 ppm of calcium stearate, 1500 ppm of Irganox 1010, 500 ppm ofUltranox 626, and 675 ppm of sodium benzoate; a 30 mm twin-screwextruder was used at an extrusion temperature of 205° C. Samples 21-24were made by dry blending neat polymer pellets with previously blendedpellets of higher plasticizer concentration (Samples 6-9) to attain thedesired plasticizer concentration.

The resin properties of these samples are listed in Tables 6-8. Theaddition of NFP in the propylene polymers improve melt flowability, asindicated by the significant increase of melt flow rate. The improvementof melt flowability can be characterized by the decrease of shearviscosity as a function of shear rate range, as illustrated in FIGS.11-13. In contrast to a peroxide degrading (or so called “vis-breaking”)process, the increase of melt flowability in the current invention ismainly due to the plasticizing effect of the NFP; the polymer molecularweight is unchanged. This is evident in the comparison of molecularweight distribution, as shown in FIG. 14. The improvement of meltflowability usually benefits fabrication processes (for example, fiberspinning, film casting, extrusion, and injection molding) in terms ofbetter draw-down, lower extruder torque, thin wall injection, and fastercycle time.

The NFP in the current invention provides a significant depression inthe storage modulus of propylene polymers. As illustrated in FIG. 1, thestorage modulus of plasticized propylene polymers are drasticallyreduced as a function of temperature relative to the unplasticizedpolyolefins. A propylene polymer having lower a storage modulus (or“elastic modulus”) at any particular temperature indicates betterflexibility for the end-use at that particular temperature.

The NFP in the current invention demonstrates the ability to depressT_(g) without altering the melting temperature and crystallizationtemperature of propylene polymers, as illustrated in FIGS. 5-10.Traditional methods to depress T_(g) include the incorporation ofcomonomers as in the case for the propylene copolymers, which alsodepresses the melting temperature and crystallization temperature ofpolymer. Polymers having lower T_(g) without compromising the meltingcharacteristics are very desirable and can provide better impactresistance, particularly for below freezing temperature impactresistance, while maintaining the ability for high temperature usage.The plasticized polyolefins of the present invention provide this.

The NFP in the current invention is miscible with the propylene polymer,as determined by, for example, the single T_(g) profile of theplasticized propylene homopolymer and propylene copolymer. This is showngraphically in FIGS. 2-3. The NFP in the current invention is alsomiscible with the propylene impact copolymer, as determined by, forexample, the two T_(g) profile of the plasticized propylene impactcopolymer, one being the lower T_(g) profile for the ethylene-propylenerubber phase and one being the higher T_(g) profile for the propylenepolymer phase. This is shown graphically in FIG. 4.

Summaries of injection molded properties for these samples are providedin Tables 9-11. Molded parts from the invention plasticizedpolypropylene homopolymers show a significant decrease in flexural andtensile modulus at a loading of 4 wt % PAO or isoparaffin, whilemaintaining their tensile strength, room temperature Izod impactresistance and heat deflection temperature. For comparison, moldedsamples were also prepared with erucamide (cis-13-docosenoamide fromCrompton), a common lubricant designed to reduce molded part surfacefriction of 4 wt % concentration. The effect of the erucamide on theflexural modulus is insignificant, as shown in Table 11.

The addition of NFP substantially improves the impact resistance ofmolded parts without the significant decrease of heat deflectiontemperature. For example, Gardner impact strength, at both room andfreezing temperatures, has improved from 350% to 400% for propylenehomopolymers, from 140 to 165% for propylene copolymers, and from 20 to40% for propylene impact copolymers due to the addition of 4-5 wt % ofNFP. It is anticipated that further increase of impact resistance isattainable by the increase of NFP concentration in the propylenepolymers. Other measures of impact resistance, including Izod impact atroom and freezing temperatures, are also significantly improved.

Another advantage of the current invention is that the heat deflectiontemperature of plasticized polyolefins is not compromised (eithermaintained or only slightly reduced) which is crucial for applicationsrequiring maintenance of molded article dimensions at high temperature.Further indication of toughness improvement is shown by the significantincrease of elongation at yield and break. Many applications requiregood conformability during the end-use. A higher elongation facilitatesthe compliance of molded articles to the deformation during either theconversion process or at the end-use.

The NFP also demonstrate the ability to provide substantial softnessimprovement in spunbond nonwoven fabrics, as provided by the lower“total hand” in Table 12. In many applications, particularly in personalhygiene and health care, a soft nonwoven is very desirable for skincontact comfort. The current invention not only provides the improvementin softness but also maintains the necessary tensile strength, tearresistance and fabric uniformity.

Comparison of film properties are listed in Table 13. The NFP,particularly the Isopar-V plasticized propylene homopolymer (Sample 2)provides improvement in the tear and impact resistance, as indicated bythe relatively high (relative to the unplasticized polyolefin) Elmendorftear in both machine direction (MD) and transverse direction (TD) anddart impact at both room and freezing temperatures. In addition, theoptical properties, i.e., haze and gloss, are also improved. Theimprovement offers advantages in many film applications, for examples,food packaging, stationery cover, tape, medical and electronicpackaging.

The data in tables 25 and 26 show similar benefits. Flowability isenhanced by the addition of the NFP as seen in the increase of MFR.Toughness increases as evidenced by the rise in impact properties.Softness is enhanced as seen by a drop in flexural modulus, but HDT islargely unaffected. The Tg drops can be substantial, but the meltingpoint and crystallization point remains essentially unchanged (to within1-2° C.).

Plasticizer Permanence

The loss of plasticizer as a function of time at elevated temperatureprovides a way to assess permanence of the plasticizer. The results inTable 27 for plasticized propylene random copolymer demonstrate theimportance of molecular weight of the plasticizer. The plasticizers werePAO liquids of increasing molecular weight and a white mineral oil. Eachplasticized sample was prepared by dry blending granules of thepropylene polymer with 10 wt % plasticizer, then was melt mixed using asingle-screw extruder to make pellets. A portion was compression moldedinto 0.25 mm thick sheets for emission testing conducted according toASTM D1203. Test specimens were 50 mm in diameter. The testingtemperature was 70° C. Specimens were weighed at 0, 24, 48. 139, 167,and 311 hours, and percentage of weight loss calculated. Over theprolonged time period examined, only the highest molecular weight PAOdid not show any additional weight loss than observed for the neatpolymer. Notably, the mineral oil exhibits significantly lowerpermanence than PAO liquids of comparable KV at 100° C. (>5 wt % lost at311 hr vs. 1-2 wt % lost for PAO).

Examples Made Using the Brabender Method

Samples presented in Tables 15-24 were blended using the BrabenderMethod. The data in these tables show similar benefits as those inTables 6-13. Flowability is enhanced by the addition of the NFP as seenin the increase of MFR. Low temperature toughness increases as evidencedby the rise in Notched Izod at −18° C. Softness is enhanced as seen by adrop in flexural modulus. The Tg drops can be substantial, but themelting point and crystallization point remains essentially unchanged(to within 1-2° C.).

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to many differentvariations not illustrated herein. For these reasons, then, referenceshould be made solely to the appended claims for purposes of determiningthe scope of the present invention. Further, certain features of thepresent invention are described in terms of a set of numerical upperlimits and a set of numerical lower limits. It should be appreciatedthat ranges formed by any combination of these limits are within thescope of the invention unless otherwise indicated.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted. Further, alldocuments cited herein, including testing procedures, are herein fullyincorporated by reference for all jurisdictions in which suchincorporation is permitted.

TABLE 4 List of Polymer Components in Examples component Description*commercial source znPP Z-N isotactic propylene homopolymer, 12 PP 1024E4, MFR ExxonMobil Chemical mPP-1 metallocene isotactic propyleneAchieve ™ 3854, homopolymer, 24 MFR, T_(m) ~152° C., ExxonMobil ChemicalM_(w)/M_(n) < 2.3 mPP-2 metallocene isotactic propylene Achieve ™ 1654,homopolymer, 16 MFR, ExxonMobil Chemical M_(w)/M_(n) < 2.3 sPPsyndiotactic propylene homopolymer, 2.2 Aldrich Chemicals MFR, 93%syndiotactic, T_(m) ~125° C., M_(w) Catalog # 452149 ~174 kg/mole, M_(n)~75 kg/mole RCP-1 Z-N propylene random copolymer, 12 Clarified PP 9054,MFR, T_(m) ~152° C. ExxonMobil Chemical RCP-2 Z-N propylene randomcopolymer, 7 PP 9513, MFR, T_(m) ~146° C., ExxonMobil ChemicalM_(w)/M_(n) < 2.3 RCP-3 Z-N propylene random copolymer, 12 PP 9374 MED,MFR ExxonMobil Chemical RCP-4 Z-N propylene random copolymer, 12 PP 9574E6, MFR ExxonMobil Chemical ICP-1 Z-N propylene impact copolymer, 21 PP7684 E2, MFR, T_(m) ~163° C. ExxonMobil Chemical ICP-2 Z-N propyleneimpact copolymer, 8 MFR PP 7033, ExxonMobil Chemical ICP-3 Z-N propyleneimpact copolymer, PP 7033N, nucleated, 8 MFR ExxonMobil Chemical TPOpropylene-based thermoplastic polyolefin 70 wt % Achieve ™ 3854,containing 70 wt % metallocene isotactic 30 wt % Exact ® 4033, propylenehomopolymer and 30 wt % ExxonMobil Chemical metallocene ethylene-butenecopolymer (0.88 g/cm³ density, 0.8 MI) EP-1 metallocenepropylene-ethylene copolymer, 9 MFR, 11 wt % ethylene made according toEP 1003 814B1 using dimethylaniliniumtetrakis(pentafluorophenyl) borateand dimethylsilylbis(indenyl)hafnium dimethyl EP-2 metallocenepropylene-ethylene copolymer, 14 MFR, 14 wt % ethylene made according toEP 1003 814B1 using dimethylaniliniumtetrakis(pentafluorophenyl) borateand dimethylsilylbis(indenyl)hafnium dimethyl PB isotactic 1-butenehomopolymer, 0.4 MI, Aldrich Chemicals T_(m) ~125° C., Catalog # 189391M_(w) ~570 kg/mole *“Z-N” indicates a Ziegler-Natta type catalyst usedfor synthesis; “metallocene” indicates a metallocene type catalyst usedfor synthesis

TABLE 5a List of Non-Functional Plasticizer (NFP) Components in ExamplesComponent Description commercial source Rudol white mineral oil CromptonFreezene 200 white mineral oil Crompton ParaLux 6001R paraffinic processoil Chevron Isopar V isoparaffinic hydrocarbon fluid ExxonMobil ChemicalNorpar 15 normal paraffinic hydrocarbon ExxonMobil Chemical fluid ExxsolD130 dearomatized aliphatic ExxonMobil Chemical hydrocarbon fluid SHF-21PAO liquid ExxonMobil Chemical SHF-41 PAO liquid ExxonMobil ChemicalSHF-61 PAO liquid ExxonMobil Chemical SHF-82 PAO liquid ExxonMobilChemical SHF-101 PAO liquid ExxonMobil Chemical SHF-403 PAO liquidExxonMobil Chemical SuperSyn 2150 PAO liquid ExxonMobil ChemicalSuperSyn PAO liquid ExxonMobil Chemical 23000 CORE 2500 Group Ibasestock ExxonMobil Chemical EHC 110 Group II basestock ExxonMobilChemical VISOM 6 Group III basestock ExxonMobil Chemical VHVI-8 GroupIII basestock PetroCanada GTL6/MBS Group III basestock ExxonMobilChemical GTL14/HBS Group III basestock ExxonMobil Chemical TPC 137polyisobutylene liquid Texas Petrochemicals Lucant HC-10 Blend of deceneoligomer with Mitsui Chemicals an ethylene/α-olefin liquid AmericaC-9900 polybutene liquid Infineum

TABLE 5b Properties of Non-Functional Plasticizer (NFP) Components inExamples specific KV, KV, gravity 40° C. 100° C. VI pour point approx.60° F. = Component (cSt) (cSt) (—) (° C.) Mn (g/mole) Cn 15.6° C. Rudol29 5 103 −24   400 28 0.86  (25° C.) Freezene 39 5 38 −42   350 25 0.882200 (25° C.) ParaLux 116 12 99 −12   580 41 0.872 6001R (60° F.) IsoparV 9 — N.D. −63   240^(#) 17 0.82  (60° F.) Norpar 15 2 — N.D. 7  210^(#) 15 0.77  (60° F.) Exxsol 4 — N.D. −6   250^(#) 18 0.83  D130(60° F.) SHF-21 5 <2 N.D. −66   280^(#) 20 0.798 (60° F.) SHF-41 19 4126 −66   450^(#) 32 0.820 (60° F.) SHF-61 31 6 138 −57   540^(#) 380.827 (60° F.) SHF-82 48 8 139 −48   640^(#) 46 0.833 (60° F.) SHF-10166 10 137 −48   720^(#) 51 0.835 (60° F.) SHF-403 396 39 147 −36  1,700⁺120 0.850 (60° F.) SuperSyn 1,500 150 218 −33  3,700⁺ 260 0.850 2150(60° F.) SuperSyn 35,000 2,800 360 −9 18,800⁺ 1,340 0.855 23000 (60° F.)CORE 490 32 95 −6   800* 57 0.896 2500 (60° F.) EHC 110 99 11 95 −12  500* 36 0.860 (60° F.) VISOM 6 35 7 148 −18   510* 36 0.836 (60° F.)VHVI-8 50 8 129 −12   560 40 0.850 (60° F.) GTL6/MBS 30 6 156 −18   510*36 0.823 (60° F.) GTL14/HBS 95 14 155 −24   750* 53 0.834 (60° F.) TPC137 30 6 132 −51   350 25 0.845 (60° F.) Lucant 60 10 150 −53   590 420.826 HC-10 (20° C.) C-9900 140 12 60 −36   540 38 0.846 (60° F.) N.D. =not defined, due to KV at 100° C. <2 cSt. Mn reported by manufacturer orestimated according to ASTM D2502, except as indicated: *estimated byfreezing point depression, ^(#)measured by GC, ⁺measured by GPC.

TABLE 6 Resin properties of plasticized mPP-1 propylene homopolymerSample No. 1 2 3 4 5 6 7 8 9 NFP none Isopar-V SHF- SHF- SuperSyn-Isopar-V SHF- SuperSyn- SuperSyn- 101 403 2150 403 2150 23000Concentration of NFP 0 4 4 4 4 10 10 10 10 (wt %) Resin Properties MFR23 32 29 29 29 51 45 39 37 Melting Temperature 152 151 153 152 153 152151 152 152 (° C.) Crystallization 115 115 118 118 118 115 116 115 115Temperature (° C.) Glass Transition 4 −1 −1 0 2 −11 −5 −3 1 Temperature(° C.)

TABLE 7 Resin properties of plasticized RCP-1 propylene random copolymerSample No. 10 11 12 13 14 NFP None Isopar-V SHF- SHF- SuperSyn- 101 4032150 Concentration of NFP 0 5 5 5 5 (wt %) Resin Properties MFR 12 16 1615 15 Melting Temperature (° C.) 152 152 152 152 152 CrystallizationTemperature 122 121 121 121 121 (° C.) Glass Transition 1 −7 −5 −3 −1Temperature (° C.)

TABLE 8 Resin properties of plasticized ICP-1 propylene impact copolymerSample No. 15 16 17 18 19 NFP none Isopar- SHF- SHF- SuperSyn- V 101 4032150 Concentration of 0 5 5 5 5 NFP (wt %) Resin Properties Melt FlowRate 23 32 29 29 29 Melting Temperature 163 162 162 162 162 (° C.)Crystallization 119 120 120 120 121 Temperature (° C.) Glass Transition−53, 5.2 −55, −3 −56, −4 −50, −1 −52, 1 Temperature (° C.)

TABLE 9 Molded part properties of plasticized mPP-1 propylenehomopolymer Sample No. 1 2 3 4 5 NFP: none Isopar V SHF-101 SHF-403SuperSyn- 2150 Concentration of NFP (wt %) 0 4 4 4 4 Optical PropertiesHaze (%) 65 62 65 61 64 Gloss @ 45° 85 87 86 85 86 Mechanical PropertiesTensile Strength @ Yield (kpsi) 4.9 4.4 4.5 4.5 4.6 Elongation @ Yield(%) 9 12 11 11 10 Flexural Modulus, 1% Secant 200 155 175 177 179 (kpsi)Heat Deflection Temperature @ 105 101 108 107 104 66 psi (° C.) RockwellHardness (R-Scale) 104 97 99 99 99 Impact Properties Notched Izod Impact@ 23° C. (ft- 0.4 0.7 0.6 0.6 0.5 lb/in) Gardner Impact Strength @ 23°C. 31 153 166 164 141 (in-lb) Gardner Impact Strength @ 0° C. —^(a) 14<8^(b) <8^(b) <8^(b) (in-lb) ^(a)Samples too brittle to perform thistest. ^(b)Samples failed at the lowest hammer weight.

TABLE 10 Molded part properties of plasticized RCP-1 propylene randomcopolymer Sample No. 10 11 12 13 14 NFP: None Isopar V SHF-101 SHF-403SuperSyn- 2150 Concentration of NFP (wt %) 0 5 5 5 5 Optical PropertiesHaze (%) 8.2 10.3 8.7 11.7 11.6 Gloss @ 45° 80 81 79 75 76 MechanicalProperties Tensile Strength @ Yield (kpsi) 5.0 4.4 4.4 4.4 4.4Elongation @ Yield (%) 9 14 13 11 11 Elongation @ Break (%) 185 754 559259 196 Flexural Modulus, 1% Secant 205 141 158 166 173 (kpsi) HeatDeflection Temperature @ 87 84 85 77 77 66 psi (° C.) Impact PropertiesNotched Izod Impact @ 23° C. (ft- 0.9 2.0 1.2 1.2 1.2 lb/in) ReversedNotched Izod Impact @ 3.9 12.6 12.4 10.5 9.0 −18° C. (ft-lb/in) GardnerImpact Strength @ 23° C. 83 203 207 201 219 (in-lb)

TABLE 11 Molded part properties of plasticized ICP-1 propylene impactcopolymer Sample No. 15 16 17 18 19 NFP: None Isopar V SHF-101 SHF-403SuperSyn- 2150 Concentration of NFP (wt %) 0 5 5 5 5 MechanicalProperties Tensile Strength @ Yield (kpsi) 3.3 3.0 3.0 3.0 3.0Elongation @ Yield (%) 5 12 10 8 8 Elongation @ Break (%) 125 230 185120 110 Flexural Modulus, 1% Secant 163 112 124 132 135 (kpsi) HeatDeflection Temperature @ 95 81 88 84 86 66 psi (° C.) Impact PropertiesNotched Izod Impact @ 23° C. (ft- 4.8 6.5 6.0 3.9 3.5 lb/in) GardnerImpact Strength @ −29° C. 123 170 165 159 148 (in-lb)

TABLE 12 Molded part properties of plasticized mPP-1 propylenehomopolymer Sample No. 20 21 22 23 24 NFP None Isopar V SHF-403SuperSyn- Erucamide 23000 Concentration of NFP (%) 0 4 4 4 4 ResinProperties MFR 24 35 33 30 23 Mechanical Properties Tensile Strength @Yield (kpsi) 4.7 4.5 4.4 4.5 4.5 Elongation @ Yield (%) 9 11 11 10 11Flexural Modulus, 1% Secant 190 155 170 180 188 (kpsi) Heat DeflectionTemperature @ 92 94 90 90 89 66 psi (° C.) Impact Properties NotchedIzod Impact @ 23° C. (ft- 0.4 0.5 0.3 0.4 0.4 lb/in) Reverse NotchedIzod Impact @ −18° C. 2.7 3.1 3.0 n/a n/a (ft-lb/in)

TABLE 13 Softness properties of spunbond nonwoven fabrics made ofplasticized mPP-1 propylene homopolymer Sample No. 1 2 3 4 5 NFP: noneIsopar V SHF-101 SHF-403 SuperSyn- 2150 Concentration of NFP (%) 0 4 4 44 Fabric Properties Peak Load (lbs) MD/TD 9.4/4.8 8.0/4.4 7.8/4.18.3/4.1 7.5/3.9 Elongation @ Break (%) MD/TD 76/77 65/76 58/67 72/7364/73 Elmendorf Tear (g/basis weight) 17 19 15 18 20 TD Total Hand(grams) 31 32 24 21 15 Properties per total hand. Total hand is based onmeasurements on fabrics at 25 gsm (grams per square meter).

TABLE 14 Cast film properties of plasticized mPP-1 propylene homopolymerSample No. 1 2 3 4 5 NFP: none Isopar V SHF-101 SHF-403 SuperSyn- 2150Concentration of NFP (%) 0 4 4 4 4 Optical Properties Haze (%) 8.8 6.216.7 14.7 10.5 Gloss 68 70 57 58 65 Mechanical Properties 1% Sec.Modulus (kpsi) MD/TD 140/130 84/86 119/120 133/121 120/115 TensileStrength @ Break (kpsi) 7.6/7.8 7.5/7.1 7.1/7.5 7.2/7.0 7.0/6.9 MD/TDElongation @ Break (%) MD/TD 730/728 725/680 770/792 785/765 738/739Elmendorf Tear (g/mil) MD 29/32 54/58 17/19 17/18 22/24 Puncture(lb/mil) 9.0 8.1 8.6 8.6 9.2 Puncture Energy (in · lb/mil) 18 21 19 1720 Total Energy Dart Impact (ft · lb) @ 23° C. 0.4 1.9 0.6 0.7 0.6 @−15° C. 0.04 0.07 0.09 0.09 0.05 Film properties are based on 2 milthickness.

TABLE 15a Tensile modulus and yield properties for plasticized znPPpropylene homopolymer Plasticizer Young's Yield Yield Energy to contentModulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi) (%)(ft-lbf) — 0 130.2 4934 12.4 21.0 Rudol 5 92.1 4578 17.8 27.3 Rudol 1075.2 3947 21.6 28.5 SHF-101 5 98.5 4614 17.3 26.9 SHF-101 10 78.9 384423.3 31.2 SHF-101 20 48.7 2658 44.1 41.8 SHF-403 5 102.2 4547 16.9 26.5SHF-403 10 86.4 4006 20.0 27.3 SuperSyn 2150 5 108.8 4736 16.1 26.4SuperSyn 2150 10 88.5 4131 19.3 26.9 Isopar V 5 93.4 4716 17.8 28.0IsoPar V 10 70.3 4100 20.9 28.0 Norpar 15 5 90.3 4627 17.7 27.2 Norpar15 10 80.4 4304 20.5 28.7 Exxsol D130 5 87.8 4628 18.3 28.1 Exxsol D13010 71.5 4038 21.9 29.0 CORE 2500 5 103.3 4720 17.0 27.2 EHC 110 5 98.94680 17.6 27.9 VISOM 6 5 92.4 4576 17.8 27.3 VHVI-8 5 92.4 4577 17.827.4 GTL6/MBS 5 92.3 4526 18.6 28.2 GTL14/HBS 5 97.1 4525 18.3 28.2 TPC137 5 94.5 4617 18.3 28.6 Lucant HC-10 5 97.9 4701 17.8 28.3 C-9900 5100.3 4641 17.6 27.8

TABLE 15b Tensile break properties for plasticized znPP propylenehomopolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 3428 639 72.5 Rudol5 3080 643 71.2 Rudol 10 3093 663 69.9 SHF-101 5 3121 700 77.5 SHF-10110 3003 683 71.6 SHF-101 20 2632 53 4.3 SHF-403 5 3003 608 67.3 SHF-40310 2953 620 65.2 SuperSyn 2150 5 3027 521 58.5 SuperSyn 2150 10 2875 41343.7 Isopar V 5 3212 672 75.2 IsoPar V 10 3380 717 76.9 Norpar 15 5 3516714 79.9 Norpar 15 10 3451 678 73.8 Exxsol D130 5 3339 708 78.6 ExxsolD130 10 3482 693 74.1 CORE 2500 5 3092 741 81.8 EHC 110 5 3142 690 76.7VISOM 6 5 3146 687 76.4 VHVI-8 5 3190 696 78.4 GTL6/MBS 5 3484 699 78.4GTL14/HBS 5 3235 687 76.6 TPC 137 5 3195 725 79.7 Lucant HC-10 5 3128699 78.3 C-9900 5 3276 698 77.1

TABLE 15c Flexure and Notched Izod impact properties for plasticizedznPP propylene homopolymer −18° C. RNI* Plasticizer 1% Secant 2% Secantimpact content Modulus Modulus resistance Plasticizer type (wt %) (kpsi)(kpsi) (ft-lb/in) — 0 189.6 171.5 2.7 Rudol 5 145.4 128.7 4.3 Rudol 10107.9 94.7 10.1 SHF-101 5 153.8 135.7 4.7 SHF-101 10 116.0 101.2 13.0SHF-101 20 65.8 57.7 6.3 SHF-403 5 163.8 145.2 3.0 SHF-403 10 123.4107.9 8.7 SuperSyn 2150 5 170.2 151.5 3.1 SuperSyn 2150 10 132.2 115.87.2 Isopar V 5 145.6 128.9 3.6 IsoPar V 10 109.2 96.3 10.2 Norpar 15 5143.6 126.8 8.2 Norpar 15 10 120.8 106.0 12.1 Exxsol D130 5 138.7 122.17.8 Exxsol D130 10 106.8 94.3 14.7 CORE 2500 5 155.4 137.8 2.8 EHC 110 5146.6 129.6 3.3 VISOM 6 5 147.6 130.1 7.7 VHVI-8 5 147.3 130.0 5.9GTL6/MBS 5 144.4 126.8 8.5 GTL14/HBS 5 160.8 140.2 7.4 TPC 137 5 145.5128.8 6.2 Lucant HC-10 5 148.5 130.5 6.2 C-9900 5 146.7 129.9 3.2*Results were obtained using the Reversed Notched Izod testing protocol(ASTM D256E).

TABLE 15d Rheological properties for plasticized znPP propylenehomopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa ·s) (s) N (g/10 min) — 0 2243 0.075 0.325 11.51 Rudol 5 Rudol 10 13340.057 0.328 32.22 SHF-101 5 1786 0.067 0.324 SHF-101 10 1311 0.053 0.31131.75 SHF-101 20 753 0.039 0.309 SHF-403 5 1827 0.068 0.323 18.99SHF-403 10 1366 0.055 0.314 29.01 SuperSyn 2150 5 1822 0.069 0.323 17.93SuperSyn 2150 10 1385 0.056 0.323 Isopar V 5 1876 0.068 0.329 IsoPar V10 1414 0.059 0.332 28.74 Norpar 15 5 1943 0.071 0.334 Norpar 15 10 16980.069 0.335 28.85 Exxsol D130 5 1927 0.071 0.331 16.78 Exxsol D130 101583 0.063 0.327 CORE 2500 5 EHC 110 5 1835 0.069 0.327 17.52 VISOM 6 51780 0.068 0.326 18.16 VHVI-8 5 1764 0.064 0.323 20.27 GTL6/MBS 5 17450.065 0.322 GTL14/HBS 5 1828 0.069 0.322 TPC 137 5 1834 0.068 0.32723.19 Lucant HC-10 5 1776 0.066 0.318 17.10 C-9900 5 1816 0.068 0.325

TABLE 15e DSC properties for plasticized znPP propylene homopolymerT_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset, at peak,ΔH_(f), Plasticizer first first first T_(c) at second second secondPlasticizer content heating heating heating onset T_(c) at peak heatingheating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (°C.) (J/g) — 0 166.0 95.8 114.7 109.0 161.4 96.2 Rudol 5 150.8 166.9 98.6117.1 108.0 153.4 164.5 102.0 Rudol 10 150.0 163.7 87.7 116.3 109.5151.1 158.5 93.3 SHF-101 5 151.7 167.1 93.8 118.4 110.0 154.0 164.9 94.2SHF-101 10 151.2 164.7 86.6 116.6 108.7 151.6 159.4 85.4 SHF-101 20149.3 162.4 79.5 113.1 106.8 146.9 161.0 81.4 SHF-403 5 151.0 167.4 89.2117.6 109.2 154.6 166.0 93.5 SHF-403 10 152.9 165.6 86.8 117.5 110.6153.5 160.7 94.8 SuperSyn 5 151.5 167.7 102.3 118.9 110.6 154.7 165.8107.8 2150 SuperSyn 10 153.6 166.1 88.0 117.0 110.9 154.4 161.0 98.42150 Isopar V 5 148.9 166.6 92.3 116.7 110.0 154.0 164.9 101.8 IsoPar V10 149.4 163.9 82.8 116.5 107.6 153.8 164.9 95.0 Norpar 5 149.1 166.298.2 116.5 109.3 154.4 164.7 97.5 15 Norpar 10 151.6 165.3 86.7 117.5109.6 155.1 161.0 97.0 15 Exxsol 5 150.4 166.6 89.5 117.1 109.6 154.4165.2 91.6 D130 Exxsol 10 D130 CORE 5 152.4 167.6 91.5 116.0 106.5 153.2166.5 97.5 2500 EHC 110 5 150.8 167.0 91.0 116.3 108.4 153.0 165.3 98.9VISOM 6 5 151.6 167.0 94.4 117.4 108.7 153.2 165.1 101.3 VHVI-8 5 150.1167.3 87.7 116.7 109.4 153.8 164.6 96.2 GTL6/ 5 MBS GTL14/ 5 HBS TPC 1375 151.8 167.6 85.2 117.0 108.8 154.2 165.7 91.2 Lucant 5 HC-10 C-9900 5149.9 166.8 94.4 117.2 109.9 153.2 165.2 102.6

TABLE 15f DMTA properties for plasticized znPP propylene homopolymerPlasticizer E′ E′ content T_(g) at onset T_(g) at peak before T_(g) at25° C. Plasticizer type (wt %) (° C.) (° C.) Peak Area (MPa) (MPa) — 0−9.7 4.7 0.19 3199 1356 Rudol 5 −39.4 −5.2 0.61 3250 714 Rudol 10 −51.5−10.4 0.70 4040 919 SHF-101 5 −44.0 −5.9 0.51 3201 915 SHF-101 10 −54.9−12.1 0.65 3776 986 SHF-101 20 −78.7 −36.9 0.94 3209 522 SHF-403 5 −39.0−3.8 0.45 3056 739 SHF-403 10 −45.2 −7.0 0.62 3001 726 SuperSyn 2150 5−36.9 −0.5 0.26 3047 929 SuperSyn 2150 10 −41.5 −6.9 0.49 2829 685Isopar V 5 −33.5 −4.6 0.41 2681 853 IsoPar V 10 −46.9 −10.7 0.73 3437673 Norpar 15 5 −46.1 −9.0 0.38 4037 1210 Norpar 15 10 −46.6 −16.4 0.573623 1034 Exxsol D130 5 −40.2 −9.4 0.60 2973 723 Exxsol D130 10 CORE2500 5 −34.3 −0.7 0.36 3716 1170 EHC 110 5 −36.3 −3.1 0.47 3193 743VISOM 6 5 −47.3 −6.4 0.47 3782 1009 VHVI-8 5 −39.7 −8.2 −0.56 3459 847GTL6/MBS 5 GTL14/HBS 5 TPC 137 5 −38.7 −5.25 0.45 2836 784 Lucant HC-105 −39 −5.2 0.39 3165 762 C-9900 5 −33.5 −5 0.46 2808 835.6

TABLE 16a Tensile modulus and yield properties for plasticized mPP-1propylene homopolymer Plasticizer Young's Yield Yield Energy to contentModulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi) (%)(ft-lbf) — 0 132.3 4983 11.3 18.9 Rudol 10 68.9 3852 20.5 26.5 Freezene200 10 65.6 3930 20.5 26.9 SHF-403 5 88.1 4338 15.5 22.9 SHF-403 10 70.93888 18.8 25.1 CORE 2500 10 70.0 3869 18.7 24.6 VISOM 6 10 59.1 357421.3 25.9 C-9900 10 65.6 3778 20.3 26.0

TABLE 16b Tensile break properties for plasticized mPP-1 propylenehomopolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 3336 654 69.1 Rudol10 4307 853 92.1 Freezene 200 10 4414 875 95.4 SHF-403 5 4375 857 92.6SHF-403 10 4235 866 92.7 CORE 2500 10 4234 858 91.2 VISOM 6 10 4150 85188.1 C-9900 10 4249 906 95.3

TABLE 16c Flexure and Notched Izod impact properties for plasticizedmPP-1 propylene homopolymer Plasticizer 1% Secant 2% Secant −18° C. RNI*content Modulus Modulus impact resistance Plasticizer type (wt %) (kpsi)(kpsi) (ft-lb/in) — 0 180.4 165.8 2.5 Rudol 10 99.6 89.5 10.2 Freezene200 10 102.6 91.8 5.7 SHF-403 5 156.9 141.3 2.6 SHF-403 10 120.5 106.95.8 CORE 2500 10 114.3 101.5 4.4 VISOM 6 10 106.3 94.4 13.3 C-9900 10104.9 93.8 5.8 *Results were obtained using the Reversed Notched Izodtesting protocol (ASTM D256E).

TABLE 16d Rheological properties for plasticized mPP-1 propylenehomopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa.s)(s) n (g/10 min) — 0 830 0.012 0.190 25.54 Rudol 10 515 0.009 0.15550.21 Freezene 200 10 519 0.009 0.185 47.04 SHF-403 5 SHF-403 10 5210.009 0.135 CORE 2500 10 527 0.009 0.137 VISOM 6 10 C-9900 10 515 0.0090.173

TABLE 16e DSC properties for plasticized mPP-1 propylene homopolymerT_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at on set, at peak,ΔH_(f), Plasticizer first first first T_(c) at second second secondPlasticizer content heating heating heating onset T_(c) at peak heatingheating heating type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (°C.) (J/g) — 0 151.4 79.1 109.1 104.2 149.5 89.2 Rudol 10 133.0 149.670.2 107.1 102.6 138.7 105.9 77.5 Freezene 10 133.3 149.4 73.7 107.4104.0 138.6 147.5 85.2 200 SHF-403 5 SHF-403 10 135.9 151.3 74.7 108.6103.5 139.9 149.2 82.6 CORE 2500 10 134.8 151.4 74.5 107.1 101.2 139.3147.4 78.3 VISOM 6 10 C-9900 10

TABLE 16f DMTA properties for plasticized mPP-1 propylene homopolymerPlasticizer E′ E′ content T_(g) at onset T_(g) at peak before T_(g) at25° C. Plasticizer type (wt %) (° C.) (° C.) Peak Area (MPa) (MPa) — 0−15.4 5.6 0.19 2179 807 Rudol 10 −46.2 −7.9 0.62 3894 898 Freezene 20010 −36.3 −5.2 0.64 3497 571 SHF-403 5 SHF-403 10 −42.0 −6.8 0.47 2884702 CORE 2500 10 −68.0 −51.7 0.07 3472 601 VISOM 6 10 C-9900 10 −41.1−8.8 0.71 3139 673

TABLE 17a Tensile modulus and yield properties for plasticized RCP-2propylene random copolymer Plasticizer Young's Yield Yield Energy tocontent Modulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi)(%) (ft-lbf) — 0 75.2 3997 17.0 23.0 Rudol 10 39.8 3126 26.5 27.6ParaLux 6001R 10 45.8 3156 26.0 27.8 SuperSyn 2150 10 49.6 3192 24.727.0 EHC 110 10 41.1 3129 26.5 27.9 VISOM 6 10 38.5 3114 26.7 27.8GTL14/HBS 10 43.6 3160 26.5 28.2

TABLE 17b Tensile break properties for plasticized RCP-2 propylenerandom copolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 4422 710 82.0 Rudol10 4883 1057 127.1 ParaLux 6001R 10 3919 763 79.4 SuperSyn 2150 10 45681006 116.7 EHC 110 10 4793 1039 123.8 VISOM 6 10 4751 1096 128.8GTL14/HBS 10 4865 1052 127.4

TABLE 17c Flexure and Notched Izod impact properties for plasticizedRCP-2 propylene random copolymer Plasticizer 1% Secant 2% Secant −18° C.RNI* content Modulus Modulus impact resistance Plasticizer type (wt %)(kpsi) (kpsi) (ft-lb/in) — 0 121.2 109.7 3.0 Rudol 10 67.8 60.2 26.2ParaLux 6001R 10 75.2 66.8 20.9 SuperSyn 2150 10 82.6 72.4 16.2 EHC 11010 70.4 62.6 21.6 VISOM 6 10 71.8 63.6 30.0** GTL14/HBS 10 76.6 67.327.2 *Results were obtained using the Reversed Notched Izod testingprotocol (ASTM D256E). **Some RNI failures were incomplete breaks.

TABLE 17d Rheological properties for plasticized RCP-2 propylene randomcopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa · s)(s) n (g/10 min) — 0 4467 0.120 0.297 7.20 Rudol 10 2605 0.124 0.352ParaLux 6001R 10 19.30 SuperSyn 2150 10 2752 0.125 0.345 15.38 EHC 11010 VISOM 6 10 2514 0.114 0.345 16.59 GTL14/HBS 10

TABLE 17e DSC properties for plasticized RCP-2 propylene randomcopolymer T_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset,at peak, ΔH_(f), Plasticizer first first first T_(c) at second secondsecond content heating heating heating onset T_(c) at peak heatingheating heating Plasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (°C.) (° C.) (° C.) (J/g) — 0 149.7 67.9 104.1 99.2 146.2 77.9 Rudol 10122.0 147.0 65.2 101.7 95.2 130.1 141.2 61.5 ParaLux 6001R 10 SuperSyn2150 10 127.1 149.3 70.8 104.9 97.4 133.2 143.4 69.7 EHC 110 10 123.7148.2 67.2 101.4 94.8 130.6 144.3 64.3 VISOM 6 10 125.1 148.6 65.1 101.394.5 130.3 144.8 65.6 GTL14/HBS 10

TABLE 17f DMTA properties for plasticized RCP-2 propylene randomcopolymer Plasticizer T_(g) at T_(g) E′ E′ Plasticizer content onset atpeak Peak before T_(g) at 25° C. type (wt %) (° C.) (° C.) Area (MPa)(MPa) — 0 −19.8 −1.9 0.39 3344 1038 Rudol 10 −48.8 −10.0 1.03 3992 600ParaLux 10 −48.0 −11.5 0.87 3263 472 6001R SuperSyn 10 −39.7 −6.7 0.703086 510 2150 EHC 110 10 −46.4 −9.8 0.91 3503 464 VISOM 6 10 −59.5 −15.70.83 3425 481 GTL14/HBS 10

TABLE 18a Tensile modulus and yield properties for plasticized EP-1propylene-ethylene copolymer Plasticizer Young's Yield Yield contentModulus Stress* Strain* Plasticizer type (wt %) (kpsi) (psi) (%) — 04.23 564 24 Rudol 10 2.68 434 27 SHF-101 10 2.78 442 27 VHVI-8 10 2.74449 28 TPC 137 10 2.78 456 28 Lucant HC-10 10 2.50 453 30 C-9900 10 2.82444 27 *Compression-molded test specimens; yield determined using 10%off-set definition.

TABLE 18b Tensile break properties for plasticized EP-1 propylene-ethylene copolymer Plasticizer Break Break Energy to content stressStrain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 2896 179194.5 Rudol 10 * * * SHF-101 10 * * * VHVI-8 10 2679 1930 88.8 TPC 13710 * * * Lucant HC-10 10 2947 1883 87.7 C-9900 10 2865 1861 85.2*Majority of specimens did not break before maximum strain limitreached.

TABLE 18c Flexure properties for plasticized EP-1 propylene-ethylenecopolymer Plasticizer 1% Secant 2% Secant content Modulus ModulusPlasticizer type (wt %) (kpsi) (kpsi) — 0 5.854 5.816 Rudol 10 4.5984.456 SHF-101 10 4.668 4.448 VHVI-8 10 4.895 4.786 TPC 137 10 4.5794.439 Lucant HC-10 10 4.615 4.506 C-9900 10 4.568 4.437

TABLE 18d Rheological properties plasticized EP-1 propylene-ethylenecopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa · s)(s) n (g/10 min) — 0 2032 0.022 0.252 Rudol 10 SHF-101 10 VHVI-8 10 TPC137 10 Lucant HC-10 10 C-9900 10

TABLE 18e DSC properties for plasticized EP-1 propylene-ethylenecopolymer T_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset,at peak, ΔH_(f), Plasticizer first first first T_(c) at second secondsecond content heating heating heating onset T_(c) at peak heatingheating heating Plasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (°C.) (° C.) (° C.) (J/g) — 0 41.8 55.6 34.3 22.6 8.3 33.7 61.4 20.9 Rudol10 40.5 51.8 25.5 29.8 22.0 41.2 50.8, 19.2 67.2 SHF-101 10 38.3 51.429.0 32.2 25.1 48.6 57.8, 18.3 67.0 VHVI-8 10 TPC 137 10 Lucant HC-10 10C-9900 10

TABLE 18f DMTA properties for plasticized EP-1 propylene-ethylenecopolymer Plasticizer T_(g) T_(g) E′ E′ Plasticizer Content at onset atpeak Peak before T_(g) at 25° C. type (wt %) (° C.) (° C.) Area (MPa)(MPa) — 0 −24.5* Rudol 10 −35.5 −21.8 3.7 2515 16.1 SHF-101 10 −38.2−22.5 4.3 3196 18.7 VHVI-8 10 −38.3 −22.1 4.4 3307 36.1 TPC 137 10 −38.0−23.1 3.2 3028 26.9 Lucant 10 HC-10 C-9900 10 *As measured by DSC.

TABLE 19a Tensile modulus and yield properties for plasticized EP-2propylene-ethylene copolymer Plasticizer Young's Yield Yield contentModulus Stress* Strain* Plasticizer type (wt %) (kpsi) (psi) (%) — 01.457 246 28 Rudol 10 0.846 128 28 Freezene 200 10 1.043 181 29 SHF-40310 0.886 143 27 IsoPar V 10 0.793 124 27 Exxsol D130 10 0.833 125 28GTL6/MBS 10 1.092 189 28 *Compression-molded test specimens; yielddetermined using 10% off-set definition.

TABLE 19b Tensile break properties for plasticized EP-2 propylene-ethylene copolymer Plasticizer Break Break Energy to content stressStrain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 * * * Rudol10 * * * Freezene 200 10 * * * SHF-403 10 * * * IsoPar V 10 * * * ExxsolD130 10 * * * GTL6/MBS 10 * * * * Majority of specimens did not breakbefore maximum strain limit reached.

TABLE 19c Flexure properties for plasticized EP-2 propylene-ethylenecopolymer Plasticizer 1% Secant 2% Secant content Modulus ModulusPlasticizer type (wt %) (kpsi) (kpsi) — 0 2.354 2.267 Rudol 10 1.8561.791 Freezene 200 10 2.032 1.920 SHF-403 10 1.930 1.884 IsoPar V 101.521 1.502 Exxsol D130 10 1.775 1.733 GTL6/MBS 10 1.942 1.858

TABLE 19d Rheological properties for plasticized EP-2 propylene-ethylenecopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa · s)(s) n (g/10 min) — 0 1167 0.011 0.194 Rudol 10 Freezene 200 10 SHF-40310 IsoPar V 10 Exxsol D130 10 GTL6/MBS 10

TABLE 19e DSC properties for plasticized EP-2 propylene-ethylenecopolymer T_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset,at peak, ΔH_(f), Plasticizer first first first T_(c) at second secondsecond content heating heating heating onset T_(c) at peak heatingheating heating Plasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (°C.) (° C.) (° C.) (J/g) — 0 39.7 47.0 13.4 — — — — — Rudol 10 40.2 50.810.1 — — 44.7 56.2 3.5 Freezene 200 10 SHF-403 10 39.0 49.7 14.2 — —44.4 54.3 4.9 IsoPar V 10 Exxsol D130 10 42.1 49.5 10.2 — — — — —GTL6/MBS 10

TABLE 19f DMTA properties for plasticized EP-2 propylene-ethylenecopolymer Plasticizer T_(g) T_(g) at E′ E′ Plasticizer content at onsetpeak Peak before T_(g) at 25° C. type (wt %) (° C.) (° C.) Area (MPa)(MPa) — 0 −30.8* Rudol 10 Freezene 200 10 SHF-403 10 IsoPar V 10 ExxsolD130 10 GTL6/MBS 10 *As measured by DSC.

TABLE 20a Tensile modulus and yield properties for plasticized sPPpropylene homopolymer Plasticizer Young's Yield Yield Energy to contentModulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi) (%)(ft-lbf) — 0 36.7 2481 21.7 17.7 Rudol 10 21.9 1991 31.5 20.7 IsoPar V10 23.3 2057 28.9 19.5 VHVI-8 10 22.9 2047 32.9 22.6

TABLE 20b Tensile break properties for plasticized sPP propylenehomopolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 2321 254 19.8 Rudol10 2288 338 23.3 IsoPar V 10 2260 341 23.7 VHVI-8 10 2347 355 25.1

TABLE 20c Flexure and Notched Izod impact properties for plasticized sPPpropylene homopolymer −18° C. RNI* Plasticizer 1% Secant 2% Secantimpact content Modulus Modulus resistance Plasticizer type (wt %) (kpsi)(kpsi) (ft-lb/in) — 0 64.2 60.8 3.4 Rudol 10 39.5 37.3 5.0 IsoPar V 1041.8 39.4 4.8 VHVI-8 10 41.7 39.1 31.9** *Results were obtained usingthe Reversed Notched Izod testing protocol (ASTM D256E). **All RNIspecimens did not break.

TABLE 20d Rheological properties for plasticized sPP propylenehomopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa ·s) (s) n (g/10 min) — 0 12431 0.179 0.307 Rudol 10 6823 0.136 0.328IsoPar V 10 7445 0.143 0.325 VHVI-8 10 6652 0.131 0.327

TABLE 20e DSC properties for plasticized sPP propylene homopolymer T_(m)T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset, at peak, ΔH_(f),Plasticizer first first first T_(c) at second second second contentheating heating heating onset T_(c) at peak heating heating heatingPlasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (° C.) (° C.) (° C.)(J/g) — 0 116.9 128.9 39.0 81.9 70.7 — — — Rudol 10 IsoPar V 10 VHVI-810 114.0 127.0 34.2 80.8 72.2 116.1 127.5 33.9

TABLE 20f DMTA properties for plasticized sPP propylene homopolymer E′Plasticizer T_(g) T_(g) before E′ Plasticizer content at onset at peak Peak T_(g) at 25° C. type (wt %) (° C.) (° C.) Area (MPa) (MPa) — 0−4.8 8.4 1 2717 434 Rudol 10 −31.6 −6.7 1.8 3637 360 IsoPar V 10 −26.9−4.8 1.5 3462 373 VHVI-8 10 −35.5 −4.8 1.53 3141 221

TABLE 21a Tensile modulus and yield properties for plasticized ICP-2propylene impact copolymer Plasticizer Young's Yield Yield Energy tocontent Modulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi)(%) (ft-lbf) — 0 99.2 3766 10.7 13.3 Rudol 10 54.9 2985 23.0 23.9ParaLux 6001R 10 57.5 3022 21.8 22.9 SHF-101 10 61.3 3076 22.2 23.9Exxsol D130 10 43.9 2950 25.2 25.7 EHC 110 10 60.1 3096 22.4 24.1 TPC137 10 54.0 2959 23.0 23.8

TABLE 21b Tensile break properties for plasticized ICP-2 propyleneimpact copolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 2221 394 38.8 Rudol10 3430 763 76.0 ParaLux 6001R 10 3236 777 77.6 SHF-101 10 3572 774 78.9Exxsol D130 10 4020 1063 117.2 EHC 110 10 3474 681 68.2 TPC 137 10 3124776 76.3

TABLE 21c Flexure and Notched Izod impact properties for plasticizedICP-2 propylene impact copolymer Plasticizer 1% Secant 2% Secant −18° C.NI content Modulus Modulus impact resistance Plasticizer type (wt %)(kpsi) (kpsi) (ft-lb/in) — 0 144.1 129.7 1.1 Rudol 10 83.8 73.8 1.3ParaLux 6001R 10 86.8 76.7 1.3 SHF-101 10 96.1 82.6 1.3 Exxsol D130 1082.9 72.4 1.7 EHC 110 10 92.6 80.1 1.3 TPC 137 10 88.8 77.9 1.5

TABLE 21d Rheological properties for plasticized ICP-2 propylene impactcopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa · s)(s) n (g/10 min) — 0 4218 0.182 0.368 8.164 Rudol 10 2663 0.142 0.37022.26 ParaLux 6001R 10 30.95 SHF-101 10 Exxsol D130 10 2765 0.152 0.375EHC 110 10 2745 0.144 0.367 18.89 TPC 137 10 2438 0.110 0.359 27.11

TABLE 21e DSC properties for plasticized ICP-2 propylene impactcopolymer T_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset,at peak, ΔH_(f), Plasticizer first first first T_(c) at second secondsecond content heating heating heating onset T_(c) at peak heatingheating heating Plasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (°C.) (° C.) (° C.) (J/g) — 0 166.6 76.9 114.8 111.3 163.2 85.6 Rudol 10149.4 163.4 72.8 114.7 108.1 151.3 158.7 76.7 ParaLux 6001R 10 149.2165.1 73.1 113.2 106.1 150.4 163.6 74.6 SHF-101 10 Exxsol D130 10 EHC110 10 149.0 165.2 72.4 115.8 107 151.5 163.9 76.5 TPC 137 10 149.5166.0 72.0 116.2 106.5 152.3 164.2 76.4

TABLE 21f DMTA properties for plasticized ICP-2 propylene impactcopolymer Plasticizer Lower T_(g) Lower T_(g) Upper T_(g) Upper T_(g) E′E′ content at onset at peak Lower at onset at peak Upper before T_(g) at25° C. Plasticizer type (wt %) (° C.) (° C.) Peak Area (° C.) (° C.)Peak Area (MPa) (MPa) — 0 −56.4 −50.2 0.06 −24.5 2.9 0.20 2269 557 Rudol10 −63.5 −53.0 0.08 −41.5 −7.7 0.50 2854 514 ParaLux 6001R 10 −57.9−50.8 0.07 −39.2 −7.2 0.43 3425 689 SHF-101 10 Exxsol D130 10 −71.6−59.8 0.19 −34.2 −10.5 0.25 3515 558 EHC 110 10 −60.0 −50.6 0.07 −37.0−9.0 0.43 3116 589 TPC 137 10 −71.4 −59.7 0.11 −43.4 −13.0 0.40 3065 579

TABLE 22a Tensile modulus and yield properties for plasticized ICP-3propylene impact copolymer Plasticizer Young's Yield Yield Energy tocontent Modulus Stress Strain Yield Plasticizer type (wt %) (kpsi) (psi)(%) (ft-lbf) — 0 123.5 4151 8.5 11.1 ParaLux 6001R 10 68.2 3199 22.325.5 SuperSyn 2150 10 76.4 3319 17.0 19.6 Norpar 15 10 62.2 3236 24.527.7 GTL6/MBS 10 61.6 3207 26.1 29.7 Lucant HC-10 10 65.4 3153 24.8 27.8

TABLE 22b Tensile break properties for plasticized ICP-3 propyleneimpact copolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 2894 88 10.3ParaLux 6001R 10 2578 614 60.3 SuperSyn 2150 10 2903 588 59.2 Norpar 1510 3049 584 58.1 GTL6/MBS 10 3079 558 56.0 Lucant HC-10 10 3043 567 55.8

TABLE 22c Flexure and Notched Izod impact properties for plasticizedICP-3 propylene impact copolymer Plasticizer 1% Secant 2% Secant −18° C.NI content Modulus Modulus impact resistance Plasticizer type (wt %)(kpsi) (kpsi) (ft-lb/in) — 0 193.3 168.7 1.1 ParaLux 6001R 10 100.5 87.71.5 SuperSyn 2150 10 120.3 102.2 1.3 Norpar 15 10 101.5 87.9 2.3GTL6/MBS 10 103.2 87.9 1.8 Lucant HC-10 10 102.5 87.7 1.6

TABLE 22d Rheological properties for plasticized ICP-3 propylene impactcopolymer Plasticizer content η₀ λ MFR Plasticizer type (wt %) (Pa · s)(s) n (g/10 min) — 0 4301 0.190 0.367 9.22 ParaLux 6001R 10 2455 0.1290.354 18.77 SuperSyn 2150 10 Norpar 15 10 3151 0.161 0.378 GTL6/MBS 10Lucant HC-10 10 2452 0.128 0.361

TABLE 22e DSC properties for plasticized ICP-3 propylene impactcopolymer T_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f), at onset,at peak, ΔH_(f), Plasticizer first first first T_(c) at second secondsecond content heating heating heating onset T_(c) at peak heatingheating heating Plasticizer type (wt %) (° C.) (° C.) (J/g) (° C.) (°C.) (° C.) (° C.) (J/g) — 0 166.5 80.2 131.0 127.3 167.3 77.0 ParaLux6001R 10 150.5 165.0 75.8 118.3 114.4 154.1 164.1 76.6 SuperSyn 2150 10153.2 166.0 76.9 122.1 84.4 156.1 165.5 80.7 Norpar 15 10 GTL6/MBS 10Lucant HC-10 10

TABLE 22f DMTA properties for plasticized ICP-3 propylene impactcopolymer Plasticizer Lower T_(g) Lower T_(g) Upper T_(g) Upper T_(g) E′E′ content at onset at peak Lower at onset at peak Upper before T_(g) at25° C. Plasticizer type (wt %) (° C.) (° C.) Peak Area (° C.) (° C.)Peak Area (MPa) (MPa) — 0 −57.9 −50.0 −13.2 4.1 3369 768.4 ParaLux 6001R10 −59.3 −52.4 0.09 −35.2 −4.6 0.42 3037 661.4 SuperSyn 2150 10 −58.5−49.9 0.06 −35.3 −3.0 0.14 3297 716.3 Norpar 15 10 −59.2 −52.2 0.03−38.8 −11.2 0.36 3545 591.0 GTL6/MBS 10 Lucant HC-10 10 −66.4 −58.3 0.10−42.8 −9.1 0.40 3168 661.0

TABLE 23a Tensile modulus and yield properties for plasticized TPOpropylene- based thermoplastic olefin Plasticizer Young's Yield YieldEnergy to content Modulus Stress Strain Yield Plasticizer type (wt %)(kpsi) (psi) (%) (ft-lbf) — 0 68.7 3187 14.0 15.1 Rudol 10 38.1 224026.5 21.1 SHF-101 10 38.8 2189 25.2 19.9 IsoPar V 10 37.6 2304 26.5 21.4GTL14/HBS 10 39.6 2232 28.4 23.1

TABLE 23b Tensile break properties for plasticized TPO propylene-basedthermoplastic olefin Plasticizer Break Break Energy to content stressStrain Break Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 5154 1051116.0 Rudol 10 5165 1334 151.9 SHF-101 10 4780 1218 129.2 IsoPar V 105021 1276 141.2 GTL14/HBS 10 5148 1342 154.6

TABLE 23c Flexure and Notched Izod impact properties for plasticized TPOpropylene-based thermoplastic olefin Plasticizer 1% Secant 2% Secant−18° C. NI content Modulus Modulus impact resistance Plasticizer type(wt %) (kpsi) (kpsi) (ft-lb/in) — 0 116.0 105.8 1.0 Rudol 10 62.9 56.20.9 SHF-101 10 66.2 58.7 1.0 IsoPar V 10 61.5 55.1 1.1 GTL14/HBS 10 68.560.2 1.0

TABLE 23d Rheological properties for plasticized TPO propylene-basedthermoplastic olefin Plasticizer content η₀ λ MFR Plasticizer type (wt%) (Pa · s) (s) n (g/10 min) — 0 1675 0.014 0.207 Rudol 10 SHF-101 10IsoPar V 10 GTL14/HBS 10

TABLE 23e DSC properties for plasticized TPO propylene-basedthermoplastic olefin T_(m) T_(m) T_(m) T_(m) at onset, at peak, ΔH_(f),at onset, at peak, ΔH_(f), Plasticizer first first first T_(c) at secondsecond second content heating heating heating onset T_(c) at peakheating heating heating Plasticizer type (wt %) (° C.) (° C.) (J/g) (°C.) (° C.) (° C.) (° C.) (J/g) — 0 138.2 151.8 58.4 109.8 103.7 142.5150.1 64.0 Rudol 10 SHF-101 10 IsoPar V 10 GTL14/HBS 10

TABLE 23f DMTA properties for plasticized TPO propylene-basedthermoplastic olefin Plasticizer Lower T_(g) Lower T_(g) Upper T_(g)Upper T_(g) E′ E′ content at onset at peak Lower at onset at peak Upperbefore T_(g) at 25° C. Plasticizer type (wt %) (° C.) (° C.) Peak Area(° C.) (° C.) Peak Area (MPa) (MPa) — 0 −60.6 −45.1 0.06 −8.7 6.0 0.152867 782 Rudol 10 −68.1 −55.6 0.10 −34.2 −3.9 0.51 3169 425 SHF-101 10−65.0 51.7 0.07 −34.3 −7.0 0.30 3472 601 IsoPar V 10 −77.2 −57.8 0.14−34.7 −6.9 0.42 3657 609 GTL14/HBS 10

TABLE 24a Tensile modulus and yield properties for plasticized PB1-butene homopolymer Plasticizer Young's Yield Yield content ModulusStress Strain Plasticizer type (wt %) (kpsi) (psi) (%) — 0 55.0 * *Rudol 10 25.8 * * Norpar 15 10 26.3 * * VISOM 6 10 23.7 * * C-9900 1026.8 * * * No yield before failure.

TABLE 24b Tensile break properties for plasticized PB 1-butenehomopolymer Plasticizer Break Break Energy to content stress StrainBreak Plasticizer type (wt %) (psi) (%) (ft-lbf) — 0 5200 38 5.0 Rudol10 3289 31 2.4 Norpar 15 10 3349 31 2.5 VISOM 6 10 3238 31 2.3 C-9900 103139 25 1.8

TABLE 24c Flexure and Notched Izod impact properties for plasticized PB1- butene homopolymer Plasticizer 1% Secant 2% Secant −18° C. RNI*content Modulus Modulus impact resistance Plasticizer type (wt %) (kpsi)(kpsi) (ft-lb/in) — 0 79.7 74.0 17.7 Rudol 10 37.0 35.2 18.1** Norpar 1510 43.0 40.7 22.2** VISOM 6 10 36.6 35.2 19.2** C-9900 10 36.5 35.220.7** *Results were obtained using the Reversed Notched Izod testingprotocol (ASTM D256E). **Some NI failures were incomplete breaks.

TABLE 25a Resin properties of plasticized mPP-2 propylene homopolymer TmTm Tc Tc Tg wt % peak onset ΔHm peak onset ΔHc peak PAO (° C.) (° C.)(J/g) (° C.) (° C.) (J/g) (° C.) Control 0 152.8 142.2 109.6 123.8 127.2106.0 3.5 SHF61 3 151.8 142.5 105.9 123.6 127.1 104.3 SHF61 5 151.5142.3 102.8 122.6 126.1 100.9 SHF61 10 149.7 140.9 100.4 120.8 124.495.6 SHF101 3 151.9 142.8 104.1 123.5 127.0 103.1 −0.4 SHF101 5 151.5142.6 102.2 123.0 126.6 100.4 −2.3 SHF101 10 150.3 140.9 99.5 120.8124.3 100.3 −6.4 SHF401 3 152.2 142.7 104.3 123.5 126.9 106.3 SHF401 5151.7 142.1 102.6 122.8 126.4 100.8 SHF401 10 151.0 142.2 97.8 121.8125.5 98.8 SuperSyn 2150 3 152.2 142.2 103.1 123.3 126.7 105.2 SuperSyn2150 5 151.9 143.0 101.3 123 126.5 99.2 SuperSyn 2150 10 151.4 142.196.0 121.8 125.3 98.7

TABLE 25b Molded part properties of plasticized mPP-2 propylenehomopolymer Flex Tensile Elongation 1% Gardner NI RNI wt % strength toyield secant HDT RT RT −18° C. PAO MFR (kpsi) (%) (kpsi) (° C.) (in-lbs)(ft-lb/in) (ft-lb/in) Control 0 16.6 5.20 8.6 230 107.8 22 1.02 2.45SHF61 3 19.7 4.86 12.4 187 107.5 194 1.27 2.63 SHF61 5 22.5 4.40 15.0161 99.8 189 0.80 6.04 SHF61 10 28.1 3.89 16.6 133 98.9 206 0.92 11.30SHF101 3 19.5 4.73 12.8 188 104.1 167 0.68 2.75 SHF101 5 20.9 4.46 13.9174 105.7 209 0.72 3.19 SHF101 10 26.7 3.85 16.5 140 95.7 251 0.91 8.99SHF401 3 19.3 4.68 11.7 199 104.7 157 0.57 2.27 SHF401 5 21.4 4.39 12.7182 100.6 186 0.62 2.84 SHF401 10 26.8 3.96 14.9 153 96.9 192 0.83 5.62SuperSyn 3 19.2 4.78 10.5 205 101.4 153 0.49 2.63 2150 SuperSyn 5 21.64.53 12.1 190 104.3 182 0.64 2.78 2150 SuperSyn 10 23.4 3.99 13.4 15792.8 214 0.70 6.48 2150

TABLE 26 Molded part properties of plasticized propylene randomcopolymers RCP-3 25 wt % RCP-4 no NFP Exact ® no NFP 5 wt % 5 wt %Properties (control) 3035 (control) Isopar V SHF-101 Tensile strength @yield (psi) 4.7 3.2 4.2 4.0 4.0 Elongation @ yield (%) 12 16.7 13.4 16.717.2 Flex modulus 1% secant (kpsi) 167 102 146 108 116 HDT @ 66 psi (°C.) 84 70 78 73 72 Gardner impact @ 23° C. (in- 273 210 242 226 226 lbs)Notched Izod impact @ 23° C. 1.1 10.3 1.4 4.5 3.8 (ft-lbs/in) Haze (%) —— 9.9 8.6 10.2 RCP-3 contains 800 ppm CaSt, 800 ppm Ultanox626A, 500 ppmTinuvin 622, 2500 ppm Millad 3940 RCP-4 contains 400 ppm CaSt, 400 ppmIrganox 3114, 400 ppm Ultanox626A, 1500 ppm Millad 3940, 800 ppm Atmer129 Exact ® 3035 is a metallocene ethylene-butene copolymer (3.5 MI,0.90 g/cm3 density)

TABLE 27 Comparison of permanence of NFP in RCP-2 propylene randomcopolymer. plasticizer % weight loss over time period KV at 311 Blendcomposition 100° C. 24 hr 48 hr 139 hr 167 hr hr PP — 0.3 0.3 0.3 0.30.3 PP + 10% SHF-21 2 7.7 8.1 8.1 8.0 8.0 PP + 10% SHF-41 4 0.2 0.7 1.11.3 2.0 PP + 10% SHF-61 6 0.2 0.4 0.6 0.6 0.9 PP + 10% SHF-82 8 0.1 0.20.3 0.3 0.5 PP + 10% SHF-101 10 −0.1 0.2 0.2 0.1 0.3 PP + 10% Rudol 5 —— — — 5.4

TABLE 28 NFP content in polypropylene/NFP blends. Dry blend ex- com-traction position (wt % CRYSTAF Blend (wt % method method Polymer NFPMethod NFP) NFP) (wt % NFP) Achieve ™ SHF-101 Extruder 3 2.6 2.2 ±0.1^(a) 1654 5 4.5 4.2 ± 0.1^(a) 10 7.4 7.6 ± 0.1^(a) 20 15.4 15.2 ±0.5^(a)  PP 3155 SuperSyn Extruder 3 2.5^(b) 3.5 2150 6 5.5^(b) 6.5 PP1024 SHF-101 Brabender 5 — 5.9 10 — 10.3 20 — 21.1 PP 1024 Isopar VBrabender 5 — 3.9 10 — 8.3 PP 7033N SuperSyn Brabender 10 9.9 — 2150Norpar 15 Brabender 10 6.5 — GTL6/MBS Brabender 10 9.4 10.1 ^(a)Averageand standard deviation reported for results from triplicate CRYSTAFruns. ^(b)12 hour reflux.

1.-16. (canceled)
 17. A plasticized polybutene composition comprising:(A) one or more butene homopolymers consisting essentially of butene orbutene copolymers consisting essentially of butene and C₃ to C₈alpha-olefins having a weight average molecular weight of 30,000 to2,000,000 g/mol; (B) 0.01 to 40 wt % of one or more non-functionalizedplasticizers (“NFP”) based upon the weight of the one or more butenehomopolymers or copolymers and the NFP where the NFP comprises carbonand hydrogen and has (i) a pour point of less than −40° C., (ii) aviscosity index of 120 or more, (iii) a specific gravity of 0.700 to0.860 and (iv) a Kinematic viscosity of 1 to 200 cSt or more at 100° C.wherein elastomers are substantially absent from the composition andwhere ethylene homopolymers and copolymers having a weight averagemolecular weight of from 500 to 10,000 are substantially absent; andwherein the composition comprises less than 10 wt % of one or moretackifiers.
 18. The composition of claim 17, wherein the polybutene is abutene homopolymer with a T_(m) (second melt) of 50 to 135° C.
 19. Thecomposition of claim 17, wherein the polybutene is a copolymer of buteneand C₃ to C₈ alpha-olefins.
 20. The composition of claim 17, wherein theNFP has a pour point of −50° C. or less.
 21. The composition of claim17, wherein the NFP has a VI of 130 or more.
 22. The composition ofclaim 17, wherein the NFP has a specific gravity from 0.750 to 0.855.23. The composition of claim 17, wherein the NFP has a specific gravityfrom 0.790 to 0.850.
 24. The composition of claim 17, wherein the NFPconsists essentially of C₆ to C₂₀₀ paraffins.
 25. The composition ofclaim 17, wherein the NFP comprises oligomers of C₅ to C₁₄alpha-olefins.
 26. The composition of claim 17, wherein the NFPcomprises oligomers of C₆ to C₁₂ alpha-olefins.
 27. The composition ofclaim 17, wherein the NFP comprises oligomers of C₈ to C₁₂alpha-olefins.
 28. The composition of claim 17, wherein the NFPcomprises oligomers of 1-decene.
 29. The composition of claim 17,wherein the NFP has an M_(n) of 200 to 10,000 g/mol.
 30. The compositionof claim 25, wherein the NFP has a pour point between −40 and −90° C.31. The composition of claim 25, wherein the NFP has a viscosity indexof 140 or more.
 32. The composition of claim 17, wherein the NFPcomprises a mineral oil having a saturates level of 90% or more, asulfur content of less than 0.03%, and a viscosity index of 120 or more.33. The composition of claim 17, wherein the NFP comprises linear and orbranched paraffinic hydrocarbon compositions, produced by one or moregas to liquids process, having a number average molecular weight of 500to 20,000.
 34. The composition of claim 33, wherein the NFP has a VI of130 or more and a specific gravity of 0.790 to 0.850.
 35. Thecomposition of claim 17, wherein the NFP comprises a linear or branchedparaffinic hydrocarbon composition having a number average molecularweight of 500 to 21,000 g/mol, less than 10 wt % sidechains having 4 ormore carbons, at least 15 wt % sidechains having 1 or 2 carbons, andless than 2 wt % cyclic paraffins.
 36. The composition of claim 35,wherein the NFP has a viscosity index of 140 or more.
 37. Thecomposition of claim 17 further comprising filler.
 38. The compositionof claim 17 further comprising a slip agent.
 39. The composition ofclaim 17 further comprising a tackifier having a softening point of 80to 140° C.
 40. The composition of claim 17 further comprisingpolypropylene where the NFP is present at 1 to 15 wt %.
 41. Thecomposition of claim 17, wherein elastomers are not added to thecomposition.
 42. The composition of claim 17, wherein the glasstransition temperature of the composition decreases by at least 2° C.for every 1 wt % of NFP.
 43. The composition of claim 17, wherein theweight of the composition decreases by less than 3% when stored at 70°C. for 311 hours in a dry oven as determined by ASTM D-1203 using a 0.25mm thick sheet.
 44. A process of producing the plasticized polybutenecomposition of claim 17 comprising combining the polybutene and NFPcomponents in an extruder.
 45. An article of manufacture comprising theplasticized polybutene composition of claim 17 selected from: films,sheets, tubes, pipes, toys, furniture, playground equipment, sportingequipment, packaging, crates, containers, food and liquid storagecontainers, transparent cook and storage ware, medical devices,sterilizable medical devices and sterilization containers, labware, wireand cable jacketing, office floor mats, gaskets, adhesives, or sealants.46. A monolayer or multilayer film comprising the plasticized polybutenecomposition of claim 17 made by a method selected from: extrusion,co-extrusion, extrusion coating, lamination, blowing, or casting.
 47. Anarticle of manufacture comprising the plasticized polybutene compositionof claim 17 selected from: fibers; woven and nonwoven fabrics; drapes,gowns, filters, hygiene products, diapers, or films made from nonwovenfibers and fabrics.
 48. An article of manufacture comprising theplasticized polybutene composition of claim 17, wherein the article isselected from: automotive components, boat components, and watercraftcomponents; interior and exterior components for automobiles, trucks,boats, and other vehicles; bumpers, grills, trim parts, dashboards,instrument panels, exterior door components, hood components, spoiler,wind screen, hub caps, mirror housing, body panel, or protective sidemolding.
 49. The composition of claim 17 wherein the butene homopolymeror butene copolymer has a weight average molecular weight of 50,000 to2,000,000 g/mol.
 50. The composition of claim 17 wherein the butenehomopolymer or butene copolymer has a weight average molecular weight of90,000 to 500,000 g/mol.